CN102959019B - Method for forming multilayer coating film - Google Patents

Method for forming multilayer coating film Download PDF

Info

Publication number
CN102959019B
CN102959019B CN201180032092.6A CN201180032092A CN102959019B CN 102959019 B CN102959019 B CN 102959019B CN 201180032092 A CN201180032092 A CN 201180032092A CN 102959019 B CN102959019 B CN 102959019B
Authority
CN
China
Prior art keywords
quality
film
water
coating composition
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201180032092.6A
Other languages
Chinese (zh)
Other versions
CN102959019A (en
Inventor
今中健二
池浦幸宏
殿村浩规
北川博视
东达也
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kansai Paint Co Ltd
Original Assignee
Kansai Paint Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kansai Paint Co Ltd filed Critical Kansai Paint Co Ltd
Publication of CN102959019A publication Critical patent/CN102959019A/en
Application granted granted Critical
Publication of CN102959019B publication Critical patent/CN102959019B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/57—Three layers or more the last layer being a clear coat
    • B05D7/572—Three layers or more the last layer being a clear coat all layers being cured or baked together
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/423—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
    • C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/6266—Polymers of amides or imides from alpha-beta ethylenically unsaturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/06—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/002—Priming paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/36—Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)

Abstract

An object of the invention is to provide a method for forming a multilayer coating film with excellent smoothness, distinctness of image, and water resistance, by a 3-coat 1-bake coating method, even when preheating after the application of an aqueous first colored coating composition is omitted. The present invention provides a method for forming a multilayer coating film, including (1) applying an aqueous colored coating composition (A) to a substrate to form a colored coating film; (2) applying an effect pigment-containing aqueous coating composition (B) containing a binder component (b1), an effect pigment (b2), and a hydrophobic solvent (b3) in proportions of 15 to 30 parts by mass of effect pigment (b2) and 25 to 60 parts by mass of hydrophobic solvent (b3) relative to 100 parts by mass of the binder component (b1), to the colored coating film, without preheating the colored coating film, to form an effect coating film having a film thickness of 7 to 13 micrometers when cured; (3) applying a clear coating composition (C) to the effect coating film to form a clear coating film; and (4) heating the three coating films formed in steps (1) to (3) to simultaneously cure these three coating films.

Description

Form the method for multilayer film
Technical field
This application claims the right of priority of the 2010-152504 Japanese publication submitted on July 2nd, 2010, submission on July 9th, 2010 2010-156933 Japanese publication, the 2010-180372 Japanese publication of submission on August 11st, 2010 and the 2011-007734 Japanese publication of submission on January 18th, 2011, disclosed in it, content quotes in full in this as reference.
The present invention relates to and be coated with by 3-the method that 1-curing process forms the multilayer film with excellent smoothness, reflection sharpness and water-repellancy.The invention still further relates to the article by the method application.
Background technology
So far as the formation method of body of a motor car film, extensively adopt and be coated with by three the method that two roasting (3C2B) techniques form multilayer film.After to coated article application electrodeposition coating composition, the method comprises following operation successively, is then thermofixation: the application → baked and cured of application → preheating (the preheating) → clear coating composition of the application → baked and cured → matrix coating composition of midcoat composition.Usually, these three paintings, two roasting methods are widely used in by using the matrix coating composition containing effect pigment (glossiness pigment) film being formed and have so-called metallic color.
But in recent years for the object of saving the energy, people have considered the baked and cured operation after omitting midcoat composition application, and use roasting (3C1B) technique of 3 painting 1 comprising following operation successively: the application → baked and cured of application → preheating (the preheating) → clear coating composition of application → preheating (the preheating) → matrix coating composition of midcoat composition.For the object reducing the environmental pollution caused by the volatilization of organic solvent, set up and use water-based paint compositions to be expect especially as 3 painting 1 curing process of midcoat composition and matrix coating composition.In order to further conserve energy, the preheating procedure carried out after also expecting to omit application midcoat composition.
But, be coated with in 1 curing process making above-mentioned 3 of use midcoat composition and water-based matrix coating composition, due to use that is water-soluble or water-dispersed resin, the film formed probably water-repellancy is not enough, and water-based midcoat composition and water-based matrix coating composition formation mixolimnion cause level and smooth not and reflection is clear not.Particularly when being omitted in the preheating procedure carried out after application midcoat composition, there is serious mixing in water-based midcoat composition and the interface of water-based matrix coating composition between water-based inter coat and water-based basal body coating layer, causes the smoothness of the film formed and reflection sharpness seriously to reduce.
In order to solve these technical problems, patent documentation (PTL) 1 discloses 3 paintings 1 and bakes method of forming layered coating film, comprises application water-based successively first colored coating composition, water-based second colored coating composition and clear coating composition.The method of PTL1 comprises: application is as the water-based colored coating composition (A) of water-based the 1st colored coating composition (A), relative to the resin Composition solids content of 100 weight parts, the urethane emulsions (a) of described water-based colored coating composition (A) containing 50 weight part to 90 weight parts and the pigment component (c) of 10 weight part to 200 weight parts, and solids content is 45wt% to 65wt%; Under the film of formation is placed in normal temperature, do not carry out air blast or preheating; The viscosity of adjustment film is to 1x10 3(under 20 ° of C, and shearing rate is 0.1sec to Pa.s or higher -1); And application solids content is water-based second colored coating composition of 15wt% to 50wt%.In the method, PTL1 further discloses, and no matter composition is coated with which part (such as horizontal component or vertical component) being contained in coated article, the multilayer film obtained all has excellent molded appearance, and can not sink, composition can not form mixolimnion etc.But, even in such method of forming layered coating film, still there is the film smoothness of formation and the situation of reflection sharpness deficiency.
PTL2 relates to the method forming multilayer film, comprises following operation: form uncured middle film to coated article application water-based midcoat composition; Application water-based matrix coating composition forms uncured matrix film; Transparent paint coating composition forms uncured transparent coating; And heating uncured middle film, uncured matrix film and uncured transparent coating are three-layer coated to solidify this simultaneously.But PTL2 discloses the molded appearance considering gained film, preferably after application water-based midcoat composition, carry out preheating.This needs to carry out three heating processes, thus the method is simplified not in operation.
Reference listing
Patent documentation
PTL1: the 2004-97917 Japanese Unexamined Patent Publication
PTL2: the 2003-251276 Japanese Unexamined Patent Publication
Summary of the invention
Technical problem
Even if the object of the present invention is to provide when the preheating after application water-based first colored coating composition is omitted, also can make use first colored coating composition, water-based second colored coating composition and clear coating composition, be coated with by 3 the method that 1 curing process forms the multilayer film with excellent smoothness, reflection sharpness and water-repellancy.Another object of the present invention is to provide the article of the method application being formed multilayer film by this.
Technical scheme
The present inventor conducts in-depth research for achieving the above object, found that: by comprising to coated article application water-based successively first colored coating composition, 3 painting 1 curing process of water-based second colored coating composition and clear coating composition are formed in the method for multilayer film, when by the effect pigment containing specified quantitative and hydrophobic solvent and solids concn in specified range containing effect pigment water-based paint compositions be used as water-based second colored coating composition, and when after this painting of water-based paint compositions containing effect pigment is filled to solidification, the film thickness of acquisition falls in specified range, even if when the preheating after application water-based first colored coating composition is omitted, the multilayer film formed also can have excellent smoothness, reflection sharpness and water-repellancy.Thus complete the present invention.
More specifically, the invention provides the method forming multilayer film, carry out following operation (1) ~ (4) successively:
(1) application water-based colored coating composition (A) on coated article, forms uncured painted film;
(2) the described uncured painted film do not formed in preheating procedure (1), binder ingredients (b1) is comprised to described uncured painted film application, the water-based paint compositions (B) containing effect pigment of effect pigment (b2) and hydrophobic solvent (b3), after forming solidification, film thickness is uncured effect (gloss) film of 7 μm to 13 μm, wherein, relative to the solids content of the described binder ingredients (b1) of 100 mass parts, effect pigment (b2) is 15 mass parts to 30 mass parts, hydrophobic solvent (b3) is 25 mass parts to 60 mass parts,
(3) to described uncured effect film transparent paint coating composition (C) formed in operation (2), uncured transparent coating is formed; And
(4) described uncured painted film, described uncured effect film and the described uncured transparent coating that are formed in the operation (1) to (3) respectively of heating, solidifies that this is three-layer coated simultaneously.
Present invention also offers the article of the method application by this formation multilayer film.
Beneficial effect of the present invention
According to the method for formation multilayer film of the present invention, making 3 of use first colored coating composition, water-based second colored coating composition and clear coating composition to be coated with in 1 roasting coating process, can effectively prevent the first colored coating composition and the second colored coating composition from forming mixolimnion.Even if therefore when the preheating after application water-based first colored coating composition is omitted, the multilayer film that method of the present invention is formed still can have excellent smoothness, reflection sharpness and water-repellancy.
Embodiment
The method of formation multilayer film of the present invention will be described in more detail below:
(I) the first embodiment
As mentioned above, the invention provides the method for the formation multilayer film described in following item 1A:
Item 1A: the method forming multilayer film, carries out following operation (1) ~ (4) successively:
(1) application water-based colored coating composition (A) on coated article, forms uncured painted film;
(2) the described uncured painted film do not formed in preheating procedure (1), binder ingredients (b1) is comprised to described uncured painted film application, the water-based paint compositions (B) containing effect pigment of effect pigment (b2) and hydrophobic solvent (b3), after forming solidification, film thickness is the uncured effect film of 7 μm to 13 μm, wherein, relative to the solids content of the described binder ingredients (b1) of 100 mass parts, effect pigment (b2) is 15 mass parts to 30 mass parts, hydrophobic solvent (b3) is 25 mass parts to 60 mass parts,
(3) to described uncured effect film transparent paint coating composition (C) formed in operation (2), uncured transparent coating is formed; And
(4) described uncured painted film, described uncured effect film and the described uncured transparent coating that are formed in the operation (1) to (3) respectively of heating, solidifies that this is three-layer coated simultaneously.
Item 2A: the method for the formation multilayer film as described in item 1A, the solids content of the wherein said water-based paint compositions (B) containing effect pigment is 18 quality % to 35 quality %.
Item 3A: the method for the formation multilayer film as described in item 1A or 2A, wherein said water-based colored coating composition (A) comprises binder ingredients (a1) and titanium dioxide and/or barium sulfate, and the solids content of described binder ingredients (a1) relative to 100 mass parts, the total content of titanium dioxide and barium sulfate is 50 mass parts to 150 mass parts.
Item 4A: the method for the formation multilayer film according to any one of item 1A to 3A, wherein said binder ingredients (b1) comprises the vibrin of hydroxyl as it at least partially, wherein relative to the total content of acidic components in its starting raw material, the content of alicyclic polyprotonic acid is 20mol% to 100mol%.
operation (1)
In the operation (1) of the method for formation multilayer film of the present invention, application water-based colored coating composition (A) on coated article.
coated article
Treat that the coated article of application is not particularly limited.The example of coated article comprises the shell of the body of a motor car of such as automobile, truck, motorcycle and bus; Trolley part; The shell of the household appliances product of such as mobile telephone and stereo set.In these coated articles, the preferably shell of body of a motor car and trolley part.
The material of coated article is not particularly limited.The example of material comprises iron, aluminium, brass, copper, stainless steel, tin, galvanized steel, the steel (Zn-Al, Zn-Ni, Zn-Fe etc.) of galvanized alloy and similar metallic substance; Polyvinyl resin, acrylic resin, acrylonitrile-butadiene-styrene (ABS) (ABS) resin, polyamide resin, acrylic resin, permalon, polycarbonate resin, urethane resin, epoxy resin and similar resin, and various types of fiber-reinforced plastic (FRP) and similar plastic material; Glass, cement, concrete and similar inorganic materials; Timber; The textile material of such as paper and cloth.In these materials, preferred metal materials and plastic material.
Coated article can be that such as phosphatizing, the above-mentioned metallic substance of surface-treated of chromic salt process or composite oxides process or the vehicle body etc. to be formed by these metallic substance are carried out in metallic surface.This coated article can also be so as above metallic substance, vehicle body or the analogue that it are formed with film.
The example it being formed with the coated article of film comprises surface and is optionally processed and the body material defining bottom film thereon, and surface is optionally processed, defines the body material that bottom film also further defines middle film thereon thereon.Wherein, preferably there is the vehicle body of the bottom film using electrodeposition coating composition to be formed thereon, more preferably there is the vehicle body of the bottom film using cation electric deposition paint composition to be formed thereon.
As being coated with the water-based colored coating composition (A) being filled to aforementioned coated article, can use containing such as binder ingredients (a1) and pigment (a2), if and needed, further containing the coating composition for the additive of coating composition.
binder ingredients (a1)
Binder ingredients (a1) itself has film-forming properties, and crosslinkable or be not cross-linked.As binder ingredients (a1), the hitherto known film-forming resin being used as the binder ingredients of coating composition can be used.
The example of this film-forming resin comprises acrylic resin, vibrin, Synolac and urethane resin.Film-forming resin is preferably such as, containing crosslinkable functional group, hydroxyl, carboxyl and epoxy group(ing).
When film-forming resin contains hydroxyl, preferably the hydroxyl value of this film-forming resin is about 1mg KOH/g to 200mg KOH/g, more preferably from about 2mg KOH/g to 180mg KOH/g, and still more preferably from about 5mg KOH/g to 170mg KOH/g.When film-forming resin contains the acidic-group of such as carboxyl, preferably the acid number of this film-forming resin is about 5mg KOH/g to 150mg KOH/g, more preferably from about 10mg KOH/g to 100mg KOH/g, and still more preferably from about 15mg KOH/g to 80mg KOH/g.
linking agent
Except film-forming resin, linking agent also can be used as binder ingredients (a1).When linking agent is used as binder ingredients (a1) a part of, usually by the crosslinkable functionality containing such as hydroxyl, carboxyl or epoxy group(ing) and can by forming the resin (matrix resin) of crosslinked film as aforementioned film-forming resin with the reaction of linking agent.With regard to the water-repellancy, chipping resistance etc. of formed film, be suitable for using the crosslinkable coating compositions containing above-mentioned matrix resin and linking agent as water-based colored coating composition (A).
The example of matrix resin comprises acrylic resin, vibrin, Synolac and urethane resin.Particularly, this matrix resin is preferably the resin of hydroxyl, and the more preferably acrylic resin (a1-1 (a)) of hydroxyl and/or the vibrin (a1-2 (a)) of hydroxyl.Still more preferably, by the acrylic resin (a1-1 (a)) of hydroxyl and vibrin (a1-2 (a)) coupling of hydroxyl, to obtain the film of smoothness and the reflection sharpness with improvement.When coupling, for the total amount of the acrylic resin (a1-1 (a)) of hydroxyl and the vibrin (a1-2 (a)) of hydroxyl, the acrylic resin (a1-1 (a)) of hydroxyl is preferably about 10 quality % to 90 quality %, more preferably from about 20 quality % to 80 quality %, and still more preferably from about 30 quality % to 70 quality %; And the vibrin of hydroxyl (a1-2 (a)) is preferably about 90 quality % to 10 quality %, more preferably from about 80 quality % to 20 quality %, and still more preferably from about 70 quality % to 30 quality %.
the acrylic resin (a1-1 (a)) of hydroxyl
Can by use the polymerizable unsaturated monomer of the currently known methods copolymerization such as hydroxyl of the emulsion polymerisation process in such as water and one or more can prepare the acrylic resin (a1-1 (a)) of hydroxyl with other polymerizable unsaturated monomer of the polymerizable unsaturated monomer copolymerization of this hydroxyl.
The polymerizable unsaturated monomer of hydroxyl is the compound that per molecule has one or more hydroxyl and one or more polymerizable unsaturated bond.The example comprises (methyl) vinylformic acid and the mono-esterification product of glycol with 2 to 8 carbon atoms, such as 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 3-hydroxypropyl (methyl) acrylate and 4-hydroxybutyl (methyl) acrylate; (methyl) vinylformic acid and the 6-caprolactone modified product of mono-esterification product of glycol with 2 to 8 carbon atoms; N-hydroxymethyl (methyl) acrylamide, vinyl carbinol and there is (methyl) acrylate of terminal hydroxy group polyoxyethylene chain.They can be used alone or two or more couplings.
As mentioned above can with one or more other polymerizable unsaturated monomers of the polymerizable unsaturated monomer copolymerization of hydroxyl, the monomer enumerated in following (i) to (xix) can be used.These polymerizable unsaturated monomers can be used alone or two or more couplings.
(i) (methyl) alkyl acrylate or (methyl) acrylate base ester: such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, the just own ester of (methyl) vinylformic acid, (methyl) n-octyl, (methyl) 2-EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) tridecyl acrylate, (methyl) dodecylacrylate, (methyl) octadecyl acrylate, (methyl) vinylformic acid isooctadecane base ester, (methyl) cyclohexyl acrylate, (methyl) acrylic methyl cyclohexyl, (methyl) t-butylcyclohexyl ester, (methyl) vinylformic acid ring ten diester and (methyl) vinylformic acid three ring ester in the last of the ten Heavenly stems etc.
(ii) there is the polymerizable unsaturated monomer of isobornyl: such as, (methyl) isobornyl acrylate.
(iii) there is the polymerizable unsaturated monomer of adamantyl: such as, (methyl) vinylformic acid diamantane ester.
(iv) there is the polymerizable unsaturated monomer of tricyclic decenyl: such as, (methyl) vinylformic acid tricyclodecenyl esters etc.
V () is containing the polymerizable unsaturated monomer of aromatic nucleus: such as, (methyl) benzyl acrylate, vinylbenzene, alpha-methyl styrene, Vinyl toluene.
(vi) there is the polymerizable unsaturated monomer of alkoxysilyl: such as, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, γ-(methyl) acryloxypropyl Trimethoxy silane and γ-(methyl) acryloxypropyl triethoxyl silane etc.
(vii) there is the polymerizable unsaturated monomer of fluorinated alkyl: such as, (methyl) perfluoroalkyl acrylate of such as (methyl) perfluoroethyl butyl ethyl ester and (methyl) perfluoroethyl octyl group ethyl ester; And fluoroolefin.
(viii) there is the polymerizable unsaturated monomer of the photopolymerizable functional group of such as dimaleoyl imino: widely used in the art those.
(ix) vinyl compound: such as, NVP, ethene, divinyl, chloroprene, propionate and vinyl-acetic ester.
(x) carboxylic polymerizable unsaturated monomer: such as, (methyl) vinylformic acid, toxilic acid, β-crotonic acid and β-propyloic acrylic ester.
(xi) nitrogenous polymerizable unsaturated monomer: such as, (methyl) vinyl cyanide, (methyl) acrylamide, (methyl) vinylformic acid N, N-dimethylamino ethyl ester, (methyl) vinylformic acid N, the adducts of N-diethylamino ethyl ester, N, N-dimethylaminopropyl (methyl) acrylamide, methylene-bis (methyl) acrylamide, ethylenebis (methyl) acrylamide, (methyl) acrylate and (methyl) glycidyl acrylate and amine.
(xii) there is the polymerizable unsaturated monomer of 2 or more polymerizable unsaturated groups: such as in per molecule, (methyl) allyl acrylate and 1,6-hexylene glycol two (methyl) acrylate.
(xiii) containing the polymerizable unsaturated monomer of epoxy group(ing): such as, (methyl) glycidyl acrylate, (methyl) propenoic acid beta-methylglycidyl esters, (methyl) vinylformic acid 3,4-epoxycyclohexanecarboxylate, (methyl) vinylformic acid 3,4-epoxycyclohexyl ethyl ester, (methyl) vinylformic acid 3,4-epoxycyclohexyl propyl ester and glycidyl allyl ether.
(xiv) there is (methyl) acrylate of polyoxyethylene chain of end alkoxyl group: be widely used in those of the art.
(xv) containing sulfonic polymerizable unsaturated monomer: such as, the sodium salt of 2-acrylamide-2-methylpro panesulfonic acid, (methyl) vinylformic acid 2-Sulfoethyl esters, allyl sulphonic acid, 4-styrene sulfonic acid and above-mentioned sulfonic acid and ammonium salt.
(xvi) polymerizable unsaturated monomer of phosphorous acidic group, such as (methyl) vinylformic acid phosphoric acid ethoxylated ester (acid phosphoxyethyl (meth) acrylate), (methyl) vinylformic acid phosphoric acid propoxy-ester (acid phosphoxypropyl (meth) acrylate), poly-(oxygen ethene) glycol ester (acid phosphoxypoly (oxyethylene) glycol (meth) acrylate) of (methyl) vinylformic acid phosphorus acyloxy and poly-(oxypropylene) glycol ester (acidphosphoxypoly (oxypropylene) glycol (meth) acrylate) of (methyl) vinylformic acid phosphorus acyloxy.
(xvii) containing the polymerizable unsaturated monomer of ultraviolet radiation absorption functional group: such as, 2-hydroxyl-4-(3-methacryloxy-2-hydroxy propyloxy group) benzophenone, 2-hydroxyl-4-(3-acryloxy-2-hydroxy propyloxy group) benzophenone, 2,2 '-dihydroxyl-4-(3-methacryloxy-2-hydroxy propyloxy group) benzophenone, 2, and 2 '-dihydroxyl-4-(3-acryloxy-2-hydroxy propyloxy group) benzophenone and 2-(2 '-hydroxyl-5 '-methaciylyloxyethylphenyl)-2H-benzotriazole.
(xviii) polymerizable unsaturated monomer that UV is stable: such as, 4-(methyl) acryloxy-1, 2, 2, 6, 6-pentamethvl, 4-(methyl) acryloxy-2, 2, 6, 6-tetramethyl piperidine, 4-cyano group-4-(methyl) acrylamido-2, 2, 6, 6-tetramethyl piperidine, 1-(methyl) acryl-4-(methyl) acrylamido-2, 2, 6, 6-tetramethyl piperidine, 1-(methyl) acryl-4-cyano group-4-(methyl) acrylamido-2, 2, 6, 6-tetramethyl piperidine, 4-crotons acyloxy-2, 2, 6, 6-tetramethyl piperidine, 4-crotonoyl amino-2, 2, 6, 6-tetramethyl piperidine and 1-crotonyl-4-crotons acyloxy-2, 2, 6, 6-tetramethyl piperidine.
(xix) containing the polymerizable unsaturated monomer of carbonyl: such as, propenal, diacetone-acryloamide(DAA), diacetone methacrylamide, acetoacetoxyethyl methacrylate, formyl radical vinylbenzene and there is the vinyl alkyl ketone (such as ethenyl methyl ketone and vinyl ethyl ketone and vinyl butyl ketone) of 4-7 carbon atom.
Polymerizable unsaturated group used herein refers to the unsaturated group that can carry out radical polymerization.The example of such polymerizable unsaturated group comprises vinyl and (methyl) acryl.
Term used herein " (methyl) acrylate " refers to " acrylate or methacrylic ester ".Term " (methyl) vinylformic acid " refers to " acrylic or methacrylic acid ".Term " (methyl) acryloyl " refers to " acryloyl or methacryloyl ".Term " (methyl) acrylamide " refers to " acrylamide or Methacrylamide ".
The acrylic resin (a1-1 (a)) of hydroxyl is preferably containing amide group.Can by using the polymerizable unsaturated monomer of such as amide containing, as (methyl) acrylamide, N, N-dimethylamino-propyl (methyl) acrylamide, methylene-bis (methyl) acrylamide and ethylenebis (methyl) acrylamide, as preparing the acrylic resin of the hydroxyl of amide-containing with one of one or more other polymerizable unsaturated monomer of the polymerizable unsaturated monomer copolymerization of hydroxyl.
Relative to the total amount of monomer component, amount for the preparation of the polymerizable unsaturated monomer of the hydroxyl of the acrylic resin (a1-1 (a)) of hydroxyl is preferably about 1 quality % to 50 quality %, more preferably from about 2 quality % to 40 quality %, also more preferably from about 3 quality % to 30 quality %.
From the performance of the water-repellancy of the stability in storage of such as coating composition and gained film, the acid number of the acrylic resin (a1-1 (a)) of hydroxyl is preferably about 0.1mg KOH/g to 200mg KOH/g, more preferably from about 2mg KOH/g to 150mg KOH/g, and further preferably about 5mg KOH/g to 100mg KOH/g.
In addition, from the performance of the such as water-repellancy of gained film, the hydroxyl value of the acrylic resin (a1-1 (a)) of hydroxyl is preferably about 0.1mg KOH/g to 200mg KOH/g, more preferably from about 2mg KOH/g to 150mg KOH/g, and also more preferably from about 5mg KOH/g to 100mgKOH/g.
When water-based colored coating composition (A) acrylic resin containing hydroxyl (a1-1 (a)), relative to the solids content of binder ingredients (a1), the content of the acrylic resin (a1-1 (a)) of hydroxyl is preferably about 2 quality % to 70 quality %, more preferably from about 10 quality % to 65 quality %, and also more preferably from about 20 quality % to 60 quality %.
the vibrin (a1-2 (a)) of hydroxyl
Usually the vibrin (a1-2 (a)) of hydroxyl can be prepared by the esterification of acid constituents and alkoxide component or transesterification reaction.
This acid constituents can be the compound being typically used as the acid constituents preparing vibrin.The example of such acid constituents comprises the acid of aliphatic polybasic acids, alicyclic polyprotonic acid and aromatic polyvalent.
Usually, aliphatic polybasic acids comprises the ester that per molecule has the fatty compounds of at least two carboxyls, the acid anhydride of such fatty compounds and such fatty compounds.The example of aliphatic polybasic acids comprises succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid, octadecane diacid, citric acid and similar aliphaticpolycarboxylic acid; The acid anhydride of such aliphaticpolycarboxylic acid; And such aliphaticpolycarboxylic acid and the ester of low alkyl group with about 1 to 4 carbon atom.Such aliphatic polybasic acids can be used alone or two or more couplings.
From the smoothness of gained film, particularly preferably use hexanodioic acid and/or adipic anhydride as aliphatic polybasic acids.
Usually, alicyclic polyprotonic acid comprises the compound that per molecule has at least one alicyclic structure and at least two carboxyls; The ester of the acid anhydrides of these compounds and these compounds.Alicyclic structure is generally 4-6 ring structure.The example of alicyclic polyprotonic acid comprises 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, 4-hexanaphthene-1,2-dicarboxylic acid, 3-methyl isophthalic acid, 2-cyclohexane dicarboxylic acid, 4-methyl isophthalic acid, 2-cyclohexane dicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid and similar alicyclic polycarboxylic acid; The acid anhydride of these alicyclic polycarboxylic acids and these alicyclic polycarboxylic acids and the ester of low alkyl group with about 1 to 4 carbon atom.These alicyclic polyprotonic acids can be used alone, or two or more couplings.
From the smoothness of gained film, preferred alicyclic polyprotonic acid comprises 1,2-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid acid anhydride, 1,3-cyclohexane dicarboxylic acid, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, 4-hexanaphthene-1,2-dicarboxylic acid and 4-hexanaphthene-1,2-dicarboxylic anhydride.Wherein particularly preferably use 1,2-cyclohexane dicarboxylic acid and/or 1,2-cyclohexanedicarboxylic anhydride.
Usually, aromatic polyvalent acid comprises the aromatics that per molecule has at least two carboxyls; The ester of the acid anhydride of these aromatics and these aromatics.The example of aromatic polyvalent acid comprises phthalic acid, m-phthalic acid, terephthalic acid, naphthalene dicarboxylic acids, 4,4 '-diphenyl dicarboxylic acid, trimellitic acid, pyromellitic acid and similar aromatic multi-carboxy acid; The acid anhydride of these aromatic multi-carboxy acids and these aromatic multi-carboxy acids and the ester of low alkyl group with about 1 to 4 carbon atom.These aromatic polyvalent acid can be used alone, or two or more couplings.
Preferred aromatic polyvalent acid comprises phthalic acid, Tetra hydro Phthalic anhydride, m-phthalic acid, trimellitic acid and trimellitic anhydride.
The acid constituents except aliphatic polybasic acids, alicyclic polyprotonic acid and aromatic polyvalent acid can also be used.These other acid constituents includes but not limited to such as coco-nut oil fatty acid, cottonseed oil fatty acid, hempseed oil lipid acid, rice bran oil fatty acid, fish oil fatty acid, ready denier oil acid, soya fatty acid, linseed oil lipid acid, tung oil fatty acid, rape seed oil fatty acid, Castor Oil Fatty Acid, dehydrated castor oil fatty acid, safflower oil fatty acid and similar lipid acid; Lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, oleic acid, linolic acid, linolenic acid, M-nitro benzoic acid, contraposition p t butylbenzoic acid, heptanaphthenic acid, 10-phenyl stearic acid and similar monocarboxylic acid; And lactic acid, 3-hydroxybutyrate, 3-hydroxyl-4-ethoxybenzoic acid and similar hydroxycarboxylic acid.These acid constituentss can be used alone, or two or more couplings.
The polyvalent alcohol can preferably per molecule with at least two hydroxyls is used as above-mentioned alkoxide component.The example of these polyvalent alcohols comprises ethylene glycol, propylene glycol, glycol ether, 1, ammediol (trimethylene glycol), Tetraglycol 99, triglycol, dipropylene glycol, 1, 4-butyleneglycol, 1, 3-butyleneglycol, 2, 3-butyleneglycol, 1, 2-butyleneglycol, 3-methyl isophthalic acid, 2-butyleneglycol, 2-butyl-2-ethyl-1, ammediol, 1, 2-pentanediol, 1, 5-pentanediol, 1, 4-pentanediol, 2, 4-pentanediol, 2, 3-dimethyl-1, ammediol, tetramethylene glycol, 3-methyl-4, 3-pentanediol, 3-methyl isophthalic acid, 5-pentanediol, 2, 2, 4-trimethylammonium-1, 3-pentanediol, 1, 6-hexylene glycol, 1, 5-hexylene glycol, 1, 4-hexylene glycol, 2, 5-hexylene glycol, neopentyl glycol, 1, 4-cyclohexanedimethanol, Tricyclodecane Dimethanol, Hydrogenated Bisphenol A, A Hydrogenated Bisphenol A F and similar glycol, by adding the lactone compound of such as 6-caprolactone to such glycol and the polylactone diol obtained, two (hydroxyethyl) terephthalate and similar esterdiol compound, the alkylene oxide adduct of dihydroxyphenyl propane, polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol and similar polyether glycol compound, glycerine, trimethylolethane, TriMethylolPropane(TMP), Glycerol dimer, triglycerin, 1, the polyvalent alcohol of 2,6-hexanetriol, tetramethylolmethane, Dipentaerythritol, three (2-hydroxyethyl) isocyanuric acid, Sorbitol Powder, mannitol and similar ternary or more, and to the poly-lactone polyol compound that the lactone compound that the polyvalent alcohol of such ternary or more adds such as 6-caprolactone obtains.
The alkoxide component except polyvalent alcohol can also be used.These other alkoxide component includes but not limited to such as methyl alcohol, ethanol, propyl alcohol, butanols, stearyl alcohol, 2-phenoxyethyl alcohol and similar monohydroxy-alcohol; And by make propylene oxide, butylene oxide ring, " Cardura E10 " (trade(brand)name, HEXION Specialty Chemicals produces; The glycidyl ester of higly branched chain saturated fatty acid of synthesis) and the alkylol cpd that obtains of similar mono-epoxy compound and acid-respons.
The preparation method of the vibrin (a1-2 (a)) of hydroxyl is unrestricted, prepared by the method by any routine.Such as, acid constituents and alkoxide component are heated in the nitrogen stream of about 150 ° of C to 250 ° of C about 5 little of 10 hours, carry out esterification or the transesterification reaction of acid constituents and alkoxide component thus, thus the vibrin of hydroxyl can be obtained.
For esterification or transesterification reaction, can by acid constituents and alkoxide component be disposable adds in reactor, or some parts can be divided to add component one or both of.Or, first can synthesize the vibrin of hydroxyl, then make it to carry out half-esterification reaction with acid anhydrides and the vibrin obtained containing carboxyl and hydroxyl.Or, can also first synthesize carboxylic vibrin, and above-mentioned alkoxide component can be added to obtain the vibrin of hydroxyl.
Known catalyzer can be used to promote esterification or transesterification reaction.The example comprises Dibutyltin oxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, zinc acetate, manganese acetate, Cobaltous diacetate, calcium acetate, plumbic acetate, tetrabutyl titanate and titanium isopropylate.
Can in resin preparation process or afterwards with the vibrin (a1-2 (a)) of the modification hydroxyls such as lipid acid, mono-epoxy compound, polyisocyanate compounds.
The example of lipid acid comprises coco-nut oil fatty acid, cottonseed oil fatty acid, hempseed oil lipid acid, rice bran oil fatty acid, fish oil fatty acid, ready denier oil acid, soya fatty acid, linseed oil lipid acid, tung oil fatty acid, rape seed oil fatty acid, Castor Oil Fatty Acid, dehydrated castor oil fatty acid Flos Carthami fatty acid oil.The example of preferred mono-epoxy compound comprise " Cardura E10 " (trade(brand)name, HEXION Specialty Chemicals produces; The glycidyl ester of the higly branched chain saturated fatty acid of synthesis).
The example of polyisocyanate compounds comprises lysinediisocyanate, hexamethylene diisocyanate, trimethylhexane diisocyanate and similar aliphatic diisocyanate compound; Hydrogenation eylylene diisocyanate, isophorone diisocyanate, methylcyclohexane-2,4-vulcabond, methylcyclohexane-2,6-vulcabond, 4,4'-methylene-bis (cyclohexyl isocyanate), 1,3-(isocyanatomethyl) hexanaphthene and similar alicyclic diisocyanate compound; Tolylene diisocyanate, xylylene diisocyanate, diphenylmethanediisocyanate and similar aromatic diisocyanate compounds; Organic polyisocyanates, as the polymeric polyisocyanate of Lysine triisocyanate and similar ternary or more unit; The adducts of these organic polyisocyanates and polyvalent alcohol, low molecular weight polyester resin, water and/or analogue; The cyclized polymer (such as isocyanuric acid ester), biuret adducts etc. of such organic polyisocyanates.These polyisocyanate compounds can be used alone, or two or more couplings.
In the vibrin (a1-2 (a)) of hydroxyl, in order to obtain the film with excellent smoothness and excellent water-repellancy, relative to the total amount of acid constituents, amount as the alicyclic polyprotonic acid in the acid constituents of initial feed is preferably about 20mol% to 100mol%, more preferably from about 25mol% to 95mol%, and even more preferably from about 30mol% to 90mol%.From providing excellent smoothness for film, particularly preferably use 1,2-cyclohexane dicarboxylic acid and/or 1,2-cyclohexane dicarboxylic acid acid anhydride as alicyclic polyprotonic acid.
The hydroxyl value of the vibrin (a1-2 (a)) of hydroxyl is preferably about 1mg KOH/g to 200mg KOH/g, more preferably from about 2mg KOH/g to 180mg KOH/g, and even more preferably from about 5mg KOH/g to 170mg KOH/g.When hydroxyl vibrin (a1-2 (a)) also have carboxyl time, the acid number of this resin is preferably about 5mg KOH/g to 150mg KOH/g, more preferably from about 10mg KOH/g to 100mg KOH/g, and even more preferably from about 15mg KOH/g to 80mg KOH/g.The number-average molecular weight of the vibrin (a1-2 (a)) of this hydroxyl is preferably about 500 to 50,000, and more preferably from about 1,000 to 30,000, and even more preferably from about 1,200 to 10,000.
When water-based colored coating composition (A) vibrin containing hydroxyl (a1-2 (a)), relative to the solids content of binder ingredients (a1), the content of the vibrin (a1-2 (a)) of hydroxyl is preferably about 2 quality % to 70 quality %, more preferably from about 10 quality % to 55 quality %, also more preferably from about 15 quality % to 45 quality %.
Linking agent can react with the crosslinkable functionality of such as hydroxyl, carboxyl, epoxy group(ing) etc. in matrix resin, thus the compound of curable water-borne colored coating composition (A).The example of linking agent comprise aminoresin, polyisocyanate compounds, dead front type polyisocyanate compounds, the compound containing epoxy group(ing), carboxylic compound, carbodiimide compound, containing hydrazides compound and containing Urea,amino-compound.Wherein preferably and the aminoresin of hydroxyl reaction, polyisocyanate compounds and dead front type polyisocyanate compounds, the compound of the carbodiimide and with carboxyl reaction.Particularly preferably aminoresin.These linking agents can be used alone or two or more couplings.
Available aminoresin comprises the part or all of methylolated aminoresin that amino group and aldehyde component reaction generate.The example of amino group comprises trimeric cyanamide, urea, benzoguanamine, methyl guanamines, steroguanamine, spiroguanamine and Dyhard RU 100.The example of aldehyde component comprises formaldehyde, paraformaldehyde, acetaldehyde and phenyl aldehyde.
Wherein part or all of methylol can also be used by the etherified methylolated aminoresin be suitable for.The example that can be used in the alcohol of etherification reaction comprises methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, 2-ethyl butanol and 2-Ethylhexyl Alcohol.
Preferably melamine resin is used as aminoresin.Methyl-etherified melamine resin particularly preferably by obtaining with the part or all of methylol of the part or all of methylolated melamine resin of methanol etherification; By the fourth etherify melamine resin obtained with the part or all of methylol of the part or all of methylolated melamine resin of butanol etherification; And the methyl-n-butyl ether melamine resin by obtaining with the part or all of methylol of methyl alcohol and the part or all of methylolated melamine resin of butanol etherification.
With regard to the water-repellancy of gained film, the weight-average molecular weight of melamine resin is preferably 400 to 6,000, and more preferably 500 to 4,000, and also more preferably 600 to 3,000.
Available commercially available melamine resin.The example of commercially available prod comprises Cymel202, Cymel203, Cymel238, Cymel251, Cymel303, Cymel323, Cymel324, Cymel325, Cymel327, Cymel350, Cymel385, Cymel1156, Cymel1158, Cymel1116 and Cymel1130 (Nihon Cytec Industries Inc. produces), U-VAN120, U-VAN20HS, U-VAN20SE60, U-VAN2021, U-VAN2028 and U-VAN28-60 (Mitsui Chemicals, Inc.'s production).
When melamine resin is used as linking agent, tosic acid, Witco 1298 Soft Acid, dinonylnaphthalene sulfonic acid and similar sulfonic acid; Mono phosphoric acid ester butyl ester, dibutyl phosphate, list-ethylhexyl dihydrogen phosphate, two-ethylhexyl dihydrogen phosphate and similar alkyl phosphate; And these acid can be used as catalyzer with the salt of aminocompound.
Polyisocyanate compounds per molecule has at least two isocyanate group.The example comprises hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, dimer acid diisocyanate, lysinediisocyanate and similar aliphatic diisocyanate compound; Hydrogenation eylylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate and similar alicyclic diisocyanate compound; Toluylene diisocya-nate, phenylene vulcabond, 4,4'-diphenylmethanediisocyanates, eylylene diisocyanate, tetramethyl xylylen vulcabond, naphthalene diisocyanate and similar aromatic diisocyanate compounds; The organic polyisocyanates compound of trivalent or more high price, such as 2-isocyanatoethyl-2,6-bis-isocyanato capronate, 3-isocyanatomethyl-1,6-hexamethylene diisocyanate, 4-isocyanatomethyl-1,8-eight methylene diisocyanate (being commonly referred to triamino-nonane triisocyanate); The dimer of these polyisocyanate compounds or tripolymer; And these polyisocyanate compounds and polyvalent alcohol, low molecular weight polyester resin or the water urethane (urethanization) under the excessive condition of isocyanate group reacts the prepolymer obtained.
Can by obtaining dead front type polyisocyanate compounds by the isocyanate group of blocking agent polyisocyanate compounds.The example of encapsulant comprises phenol, lactan, alcohol, ester, ethyl glycolate, lactate, oxime, active methylene group, mercaptan, acid amides, imide, amine, imidazoles, urea, carbamate and imines.
When polyisocyanate compounds or dead front type polyisocyanate compounds are used as linking agent, stannous octoate (tin octylate), dibutyltin diacetate, dibutyl two isocaprylic acid tin, dibutyl tin laurate, dioctyl tin diacetate, dioctyl two isocaprylic acid tin, Dibutyltin oxide, dioctyl tin oxide, dibutyl tin soap, 2 ethyl hexanoic acid lead, zinc octoate, zinc naphthenate, fatty acid zinc compound, cobalt naphthenate, calcium octoate, copper naphthenate, four (2-ethylhexyl) titanic acid ester and similar organometallic compounds; Tertiary amine; Phosphate cpds etc. can be used as catalyzer.
The compound of the carbodiimide that can use in this article be such as by the isocyanate group in polyisocyanate compounds is carried out CO2 removal reaction obtains those.The compound of these carbodiimides can directly be bought.The example of the trade(brand)name of these commodity comprises Carbodilite SV-02, Carbodilite V-02, Carbodilite V-02-L2, CarbodiliteV-04, Carbodilite E-01 and Carbodilite E-02 (Nisshinbo company (NisshinboIndustries, Inc.) system).
When water-based colored coating composition (A) is containing linking agent, from the angle of the smoothness and water-repellancy of improving gained multilayer film, relative to the total mass of matrix resin and linking agent, the content of matrix resin is about 30 quality % to 95 quality %, preferably about 50 quality % to 90 quality %, more preferably from about 60 quality % to 80 quality %; And the content of linking agent is about 5 quality % to 70 quality %, preferably about 10 quality % to 50 quality %, and more preferably from about 20 quality % to 40 quality %.
As water-based colored coating composition (A), consider the smoothness of the multilayer film of generation, reflection sharpness and water-repellancy, can advantageously use resin containing hydroxyl as matrix resin and the melamine resin thermosetting aqueous coating composition as linking agent.
pigment (a2)
Pigment (a2) can be tinting pigment, pigment extender, effect pigment etc.
The example of tinting pigment comprises titanium dioxide, zinc powder, carbon black, chrome vermillion, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinoline Azone class pigment, isoindoline class pigment, reduction class (Anthraquinones) pigment (threne pigment), perylene class pigment, bisoxazines class pigment and diketo pyrrolo-pyrrole pigment(DPP pigment).They can be used alone or two or more couplings.Wherein, preferably titanium dioxide is used as at least one of tinting pigment.
When water-based colored coating composition (A) is containing tinting pigment, relative to the binder ingredients solids content of 100 mass parts in water-based colored coating composition (A), the content of preferred tinting pigment is generally 1 mass parts to 150 mass parts, preferably 3 mass parts to 130 mass parts, and more preferably 5 mass parts to 110 mass parts.
The example of pigment extender comprises clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talcum, silicon-dioxide and white lake.They can be used alone or two or more couplings.Wherein, preferably use barium sulfate and/or talcum, and more preferably barium sulfate is used as at least one of pigment extender.
When water-based colored coating composition (A) is containing pigment extender, relative to the binder ingredients solids content of 100 mass parts in water-based colored coating composition (A), the content of pigment extender is generally 1 mass parts to 150 mass parts, preferably 3 mass parts to 130 mass parts, and more preferably 5 mass parts to 110 mass parts.
The example of effect pigment (colour lustre pigments) comprises aluminium (such as vapor deposition aluminium), the mica of the aluminum oxide of copper, zinc, brass, nickel, aluminum oxide, mica, titanium oxide coating or the aluminum oxide of iron oxide-coated, the mica of titanium oxide coating or iron oxide-coated, sheet glass and holographic pigment.They can be used alone or two or more couplings.Wherein, preferably this effect pigment is used as by being selected from aluminium, aluminum oxide, mica, the aluminum oxide of titanium oxide coating or at least one effect pigment of the mica of the aluminum oxide of iron oxide-coated and titanium oxide coating or the mica of iron oxide-coated.
Effect pigment is preferably flake.Action effect pigment, the longitudinal size of appropriate pigment is 1 μm to 100 μm, is in particular 5 μm to 40 μm, and thickness is 0.001 μm to 5 μm, is in particular 0.01 μm to 2 μm.
When water-based colored coating composition (A) comprises effect pigment, relative to the binder ingredients solids content of 100 mass parts in water-based colored coating composition (A), the content of effect pigment is generally 1 mass parts to 50 mass parts, preferably 2 mass parts to 30 mass parts, and more preferably 3 mass parts to 20 mass parts.
Consider the smoothness of the multilayer film of generation, reflection sharpness and water-repellancy, the total amount of the titanium dioxide that preferred water-based colored coating composition (A) is contained and/or barium sulfate is relative to the solids content of 100 mass parts in binder ingredients (a1), be 50 weight part to 150 weight parts, preferably 55 weight part to 130 mass parts, and more preferably 60 weight part to 120 mass parts.Particularly, relative to the solids content of 100 mass parts in binder ingredients (a1), the content of titanium dioxide is preferably 50 weight part to 150 mass parts, more preferably 55 weight part to 130 mass parts, and even more preferably 60 weight part to 120 mass parts.
If needed, water-based colored coating composition (A) can further include the additive of coating composition, such as thickening material, curing catalysts, UV absorption agent, photostabilizer, defoamer, softening agent, surface conditioner and antisettling agent.
The example of thickening material comprises the inorganic thickening agent of such as silicate, metal silicate, montmorillonite and colloidal alumina; Such as (methyl) vinylformic acid and the multipolymer of (methyl) acrylate and the agent for polyacrylic acid thickening of sodium polyacrylate; There is hydrophilic parts and hydrophobic parts, by hydrophobic parts being adsorbed the surface of pigment or emulsion particles in the coating composition or mutually being associated by hydrophobic parts and effectively strengthen the associative thickener of the viscosity in aqueous medium in per molecule; The such as cellulose thickener of carboxymethyl cellulose, methylcellulose gum and Natvosol; The protein-based thickening material of such as casein, sodium-caseinate and ammonium caseinate; The alginates thickening material of such as sodium alginate; The polyethylene base class thickening material of such as polyvinyl alcohol, Polyvinylpyrolidone (PVP) and polyvinyl benzyl ether copolymer; The such as polyethers thickening material of polyethers dialkyl, polyethers dialkyl ether and the epoxide modified thing of polyethers; The copolymer-maleic anhydride class thickening material of the partial ester (partial ester) of such as vinyl methyl ether-copolymer-maleic anhydride; The polyamide-based thickening material of such as daiamid.These thickening materials can be used alone and also can combine two or more to use.Wherein preferably use Polyacrylate thickeners and/or associative thickener.
The example of Polyacrylate thickeners comprises commercial goods, and trade(brand)name is ACRYSOLASE-60, ACRYSOL TT-615 and ACRYSOL RM-5 (production of Rohm & Haas Co., Ltd.) such as; And SN thickener613, SN thickener618, SN thickener630, SN thickener634 and SN thickener636 (San Nopco Ltd. produces).
The example of spendable associative thickener comprises commercial goods, trade(brand)name such as UH-420, UH-450, UH-462, UH-472, UH-540, UH-752, UH-756VF and UH-814N (ADEKA Co.Ltd. produces); ACRYSOL RM-8W, PrimalRM-12W, ACRYSOL RM-825 and ACRYSOL SCT-275 (Rohm & HaasCo., Ltd. company produces); And SN thickener612, SN thickener621N, SNthickener625N, SN thickener627N and SN thickener660T (San Nopco Ltd. produces).
When water-based colored coating composition (A) is containing thickening material, relative to the binder ingredients solids content of 100 mass parts in water-based colored coating composition (A), the content of thickening material is generally 0.01 mass parts to 10 mass parts, preferably 0.05 mass parts to 3 mass parts, and more preferably 0.1 mass parts to 2 mass parts.
Can by use known method mix in an aqueous medium and dispersing binder component (a1), pigment (a2) and if needs, thickening material, curing catalyst, UV absorption agent, photostabilizer, defoamer, softening agent, surface conditioner, antisettling agent and other coating composition additive prepare water-based colored coating composition (A).The example of aqueous medium comprises the mixture of deionized water and deionized water and hydrophilic organic solvent.The example of hydrophilic organic solvent comprises propylene glycol monomethyl ester.The water content of preferred water-based colored coating composition (A) is 10 quality % to 95 quality %, more preferably 20 quality % to 80 quality %, and also more preferably 30 quality % to 70 quality %.
Preferably, the solids concn of water-based colored coating composition (A) is generally 30 quality % to 80 quality %, more preferably 40 quality % to 70 quality %, and also more preferably 45 quality % to 60 quality %.
By the known method of such as aerial spraying, Airless spraying, rotary-atomizing application or showering, water-based colored coating composition (A) can be coated on the electrodeposition coating of solidification.Electrostatic can be applied during application.Wherein, preferred aerial spraying, rotary-atomizing application etc.
Consider the smoothness of the multilayer film of generation, preferably water-based colored coating composition (A) is coated with the film thickness obtained after being filled to solidification be 5 μm to 40 μm, more preferably 10 μm to 30 μm, also more preferably 15 μm to 25 μm.
operation (2)
The upper application of the film (being hereafter sometimes referred to as " painted film ") formed by water-based colored coating composition (A) of the non-preheating formed in above-mentioned operation (1) contains the water-based paint compositions (B) containing effect pigment of binder ingredients (b1), effect pigment (b2) and hydrophobic solvent (b3), relative to the solids content of the binder ingredients (b1) of 100 mass parts, effect pigment (b2) is 15 mass parts to 30 mass parts, and hydrophobic solvent (b3) is 25 mass parts to 60 mass parts.After forming solidification thus, film thickness is the uncured effect film of 7 μm to 13 μm.
binder ingredients (b1)
Binder ingredients (b1) itself has film-forming properties, and can be not crosslinkable or crosslinkable.The hitherto known film-forming resin that can be used as coating composition binder ingredients all can be used as binder ingredients (b1).
The example of film-forming resin comprises acrylic resin, vibrin, Synolac and urethane resin.Preferred film-forming resin contains the crosslinkable functional group of such as hydroxyl, carboxyl and epoxy group(ing).
In binder ingredients (b1), when film-forming resin contains hydroxyl, the hydroxyl value of preferred film-forming resin is about 1mg KOH/g to 200mg KOH/g, more preferably from about 2mg KOH/g to 180mg KOH/g, and also more preferably from about 5mg KOH/g to 170mg KOH/g.When film-forming resin contains the acidic-group of such as carboxyl, the acid number of preferred film-forming resin is about 5mg KOH/g to 150mg KOH/g, more preferably from about 10mg KOH/g to 100mg KOH/g, and also more preferably from about 15mg KOH/g to 80mg KOH/g.
Except film-forming resin, linking agent can also be used as binder ingredients (b1).When linking agent is used as binder ingredients (b1) a part of, usually by the crosslinkable functionality containing such as hydroxyl, carboxyl or epoxy group(ing) and can by forming the resin (matrix resin) of crosslinked film as above-mentioned film-forming resin with the reaction of linking agent.Consider the water-repellancy of gained film, chipping resistance etc., the suitable crosslinkable coating composition containing above-mentioned matrix resin and linking agent that uses is as the water-based paint compositions (B) containing effect pigment.
The example of matrix resin comprises acrylic resin, vibrin, Synolac and urethane resin.Particularly, matrix resin is preferably the resin of hydroxyl, and the more preferably acrylic resin (b1-1) of hydroxyl and/or the vibrin (b1-2) of hydroxyl.Vibrin (b1-2) coupling of the preferred acrylic resin by hydroxyl (b1-1) and hydroxyl is to obtain the film of smoothness and the reflection sharpness with improvement further.During coupling, relative to the total amount of the acrylic resin (b1-1) of hydroxyl and the vibrin (b1-2) of hydroxyl, the acrylic resin (b1-1) of hydroxyl is preferably about 10 quality % to 90 quality %, and more preferably from about 20 quality % to 80 quality %, the vibrin (b1-2) of hydroxyl is preferably about 90 quality % to 10 quality %, and more preferably from about 80 quality % to 20 quality %.
the acrylic resin (b1-1) of hydroxyl
Can by use the polymerizable unsaturated monomer of the currently known methods copolymerization such as hydroxyl of emulsion polymerisation process in such as water and one or more can prepare the acrylic resin (b1-1) of hydroxyl with other polymerizable unsaturated monomer of the polymerizable unsaturated monomer copolymerization of hydroxyl.
The polymerizable unsaturated monomer of the hydroxyl addressed in the explanation of the acrylic resin (a1-1 (a)) of hydroxyl can be used as this hydroxyl polymerizable unsaturated monomer or be used as one or more can with other polymerizable unsaturated monomer of the polymerizable unsaturated monomer copolymerization of hydroxyl.
Relative to the total amount of monomer component, amount for the preparation of the polymerizable unsaturated monomer of the hydroxyl of the acrylic resin (b1-1) of hydroxyl is preferably about 1 quality % to 50 quality %, more preferably from about 2 quality % to 40 quality %, also more preferably from about 3 quality % to 30 quality %.
At aspect of performance, the stability in storage of such as coating composition and the water-repellancy of gained film, the acid number of the acrylic resin (b1-1) of hydroxyl is preferably about 0.1mg KOH/g to 200mgKOH/g, more preferably from about 2mg KOH/g to 150mg KOH/g, and more preferably from about 5mgKOH/g to 100mg KOH/g.
Further, at the aspect of performance of the such as water-repellancy of gained film, the hydroxyl value of the acrylic resin (b1-1) of hydroxyl is preferably about 0.1mg KOH/g to 200mg KOH/g, more preferably from about 2mg KOH/g to 150mg KOH/g, and further preferably about 5mg KOH/g to 100mg KOH/g.
When the water-based paint compositions (B) containing effect pigment comprises acrylic resin (b1-1) of hydroxyl, relative to the solids content of binder ingredients (b1), the content of the acrylic resin (b1-1) of hydroxyl is preferably about 2 quality % to 70 quality %, more preferably from about 10 quality % to 65 quality %, and also more preferably from about 20 quality % to 60 quality %.
the vibrin (b1-2) of hydroxyl
Usually the vibrin (b1-2) of hydroxyl can be prepared by the esterification of acid constituents and alkoxide component or transesterification reaction.
The compound addressed in the explanation of the vibrin (a1-2 (a)) of hydroxyl can be used as acid constituents or alkoxide component.
The preparation method of the vibrin (b1-2) of hydroxyl is unrestricted, can be prepared by any ordinary method.Such as, under about 150 ° of C to 250 ° of C, heat acid constituents in a stream of nitrogen and alkoxide component about 5 is little of 10 hours, make acid constituents and alkoxide component carry out esterification or transesterification reaction, thus the vibrin of hydroxyl can be prepared.
For esterification or transesterification reaction, acid constituents or alkoxide component can be added reaction vessel simultaneously, or can add several times by one of described component or all.Or then the vibrin that first can synthesize hydroxyl carries out half-esterification reaction with acid anhydrides, thus obtain the vibrin containing carboxyl and hydroxyl.Also or, can first synthesize carboxylic vibrin, and above-mentioned alkoxide component can be added to obtain the vibrin of hydroxyl.
In order to promote esterification or transesterification reaction, known catalyzer can be used.The example comprises Dibutyltin oxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, zinc acetate, manganese acetate, Cobaltous diacetate, calcium acetate, plumbic acetate, tetrabutyl titanate and titanium isopropylate.
The vibrin (b1-2) of hydroxyl in resin-made for period or can modify with lipid acid, mono-epoxy compounds, polyisocyanate compounds or analogue afterwards.
The compound addressed in the explanation of the vibrin (a1-2 (a)) of hydroxyl can be used as lipid acid, mono-epoxy compounds or polyisocyanate compounds.
In order to obtain the multilayer film with excellent smoothness, reflection sharpness and water-repellancy, in the vibrin (b1-2) of hydroxyl, one of them part, relative to the total amount of acid constituents, amount as the alicyclic polyprotonic acid in the acid constituents of initial feed is preferably about 20mol% to 100mol%, more preferably from about 25mol% to 80mol%, and even more preferably from about 30mol% to 60mol%.Providing in the film with excellent smoothness, particularly preferably use 1,2-cyclohexane dicarboxylic acid and/or 1,2-cyclohexane dicarboxylic acid acid anhydride as alicyclic polyprotonic acid.
The hydroxyl value of the vibrin (b1-2) of hydroxyl is preferably about 1mg KOH/g to 200mgKOH/g, more preferably from about 2mg KOH/g to 180mg KOH/g, and even more preferably from about 5mgKOH/g to 170mg KOH/g.When the vibrin (b1-2) of hydroxyl also has carboxyl, the acid number of this resin is preferably about 5mg KOH/g to 150mg KOH/g, more preferably from about 10mgKOH/g to 100mg KOH/g, and even more preferably from about 15mg KOH/g to 80mgKOH/g.The number-average molecular weight of the vibrin (b1-2) of hydroxyl is preferably about 500 to 50,000, and more preferably from about 1,000 to 30,000, and even more preferably from about 1,200 to 10,000.
When containing water-based paint compositions (B) vibrin containing hydroxyl (b1-2) of effect pigment, relative to the solids content of binder ingredients (b1), the content of the vibrin (b1-2) of hydroxyl is preferably about 2 quality % to 70 quality %, more preferably from about 10 quality % to 55 quality %, also more preferably from about 15 quality % to 45 quality %.
The linking agent that can use in containing the water-based paint compositions (B) of effect pigment can react with the crosslinkable functionality such as such as hydroxyl, carboxyl, epoxy group(ing) in matrix resin thus solidify the compound of the water-based paint compositions (B) containing effect pigment.The example of linking agent comprise aminoresin, polyisocyanate compounds, dead front type polyisocyanate compounds, the compound containing epoxy group(ing), carboxylic compound, carbodiimide compound, containing hydrazides compound and containing Urea,amino-compound.The linking agent addressed in the explanation of water-based colored coating composition (A) all can use.Wherein, preferably with the compound of the aminoresin of hydroxyl reaction, polyisocyanate compounds and dead front type polyisocyanate compounds and the carbodiimide with carboxyl reaction.Particularly preferably aminoresin.These linking agents can be used alone or two or more couplings.
When the water-based paint compositions (B) containing effect pigment is containing linking agent, from the viewpoint of smoothness and the water-repellancy of improving gained multilayer film, relative to the total amount of matrix resin and linking agent, the content of matrix resin is about 30 quality % to 95 quality %, preferably about 50 quality % to 90 quality %, more preferably from about 60 quality % to 80 quality %, the content of linking agent is about 5 quality % to 70 quality %, preferably about 10 quality % to 50 quality %, and more preferably from about 20 quality % to 40 quality %.
As the water-based paint compositions (B) containing effect pigment, consider the smoothness of gained multilayer film, reflection sharpness and water-repellancy, use the thermofixation water-based paint compositions of the resin containing hydroxyl as matrix resin, melamine resin as linking agent advantageously.
effect pigment (b2)
The example of effect pigment (b2) comprises aluminium (such as vapor deposition aluminium), the mica of the aluminum oxide of copper, zinc, brass, nickel, aluminum oxide, mica, titanium oxide coating or the aluminum oxide of iron oxide-coated, the mica of titanium oxide coating or iron oxide-coated, sheet glass and holographic pigment.They can be used alone or two or more couplings.Wherein, be preferably used as effect raw material by being selected from aluminium, aluminum oxide, mica, the aluminum oxide of titanium oxide coating or at least one effect pigment of the mica of the aluminum oxide of iron oxide-coated and titanium oxide coating or the mica of iron oxide-coated, and particularly preferably use aluminium.
Effect pigment (b2) is preferably flake.Action effect pigment (b2), the longitudinal size being applicable to pigment is 1 μm to 100 μm, is in particular 5 μm to 40 μm, and thickness is 0.001 μm to 5 μm, is in particular 0.01 μm to 2 μm.
hydrophobic solvent (b3)
Hydrophobic solvent (b3) is contemplated to be organic solvent, and the quality that wherein this organic solvent dissolves in 100g water under 20 ° of C is 10g or less, preferred 5g or less, more preferably 1g or less.The example of these organic solvents comprises varsol, such as rubber solvent, mineral spirits, toluene, dimethylbenzene and solvent naphtha; Alcoholic solvent, such as 1-hexanol, 1-octanol, sec-n-octyl alcohol, 2-ethyl-1-hexanol, 1-decanol, phenylcarbinol, ethylene glycol list-2-ethylhexyl ether, propylene glycol list n-butyl ether, dipropylene glycol list n-butyl ether, tripropylene glycol list n-butyl ether, propylene glycol list-2-ethylhexyl ether and propylene glycol list phenyl ether; Esters solvent, such as n-butyl acetate, isobutyl acetate, Isoamyl Acetate FCC, methyl amyl acetate and ethylene glycol monomethyl ether acetate; And ketones solvent, such as methyl iso-butyl ketone (MIBK), pimelinketone, ethyl n-pentyl ketone and diisobutyl ketone.These solvents can be used alone, or two or more couplings.
In order to obtain the multilayer film of the smoothness with improvement and reflection sharpness, hydrophobic solvent (b3) is preferably hydrophobicity alcohol organic solvent, and more preferably C 7-C 14alcohols hydrophobic solvent.Particularly, at least one alcohols hydrophobic solvent being selected from 1-octanol, sec-n-octyl alcohol, 2-ethyl-1-hexanol, ethylene glycol list-2-ethylhexyl ether, propylene glycol list n-butyl ether and dipropylene glycol list n-butyl ether is preferred.
containing the preparation of the water-based paint compositions (B) of effect pigment
Relative to the solids content of the binder ingredients (b1) of 100 mass parts, the ratio of the water-based paint compositions (B) containing effect pigment contained binder ingredients (b1), effect pigment (b2) and hydrophobic solvent (b3) is effect pigment (b2) 15 mass parts to 30 mass parts, preferably 16 mass parts to 25 mass parts, and more preferably 18 mass parts to 23 mass parts, with hydrophobic solvent (b3) 25 mass parts to 60 mass parts, preferably 30 mass parts to 50 mass parts, and more preferably 35 mass parts to 45 mass parts.
If needed, the water-based paint compositions (B) containing effect pigment can comprise one or more pigment except effect pigment (b2).The example of these pigment comprises tinting pigment and pigment extender.
The example of tinting pigment comprises titanium dioxide, zinc powder, carbon black, chrome vermillion, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinoline Azone class pigment, isoindoline class pigment, reduction class (Anthraquinones) pigment, perylene class pigment, bisoxazines class pigment and diketopyrrolopyrroles pigment.They can be used alone or two or more couplings.
When the water-based paint compositions (B) containing effect pigment is containing tinting pigment, preferably containing the solids content relative to the binder ingredients (b1) of 100 mass parts in the water-based paint compositions (B) of effect pigment, content normally 1 mass parts to 100 mass parts of tinting pigment, preferably 2 mass parts to 50 mass parts, and more preferably 3 mass parts to 30 mass parts.
The example of pigment extender comprises clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talcum, silicon-dioxide and white lake, and they can be used alone or two or more couplings.
When the water-based paint compositions (B) containing effect pigment is containing pigment extender, containing in the water-based paint compositions (B) of effect pigment relative to the solids content of the binder ingredients (b1) of 100 mass parts, the content of pigment extender is generally 1 mass parts to 100 mass parts, preferably 2 mass parts to 50 mass parts, and more preferably 3 mass parts to 30 mass parts.
If needed, water-based paint compositions (B) containing effect pigment can contain the typical additives of coating composition further, such as curing catalyst, thickening material, UV absorption agent, photostabilizer, defoamer, softening agent, organic solvent, surface conditioner and antisettling agent.These additives for coating composition can be used alone or two or more couplings.The additive of the coating composition addressed when explaining water-based colored coating composition (A) can be used in.
In the method for formation multilayer film of the present invention, the solids concn containing the water-based paint compositions (B) of effect pigment is preferably 18 quality % to 35 quality %.Particularly, consider smoothness and the reflection sharpness of gained multilayer film, the solids concn containing the water-based paint compositions (B) of effect pigment is preferably 20 quality % to 30 quality %, and more preferably 23 quality % to 27 quality %.
Can by known method such as aerial spraying, Airless spraying or the rotary-atomizing spray-coating water-based paint compositions (B) containing effect pigment.Electrostatic can be applied during application.
In the method for formation multilayer film of the present invention, the film thickness after the effect curing of coating that the water-based paint compositions (B) containing effect pigment by application is formed is 7 μm to 13 μm.Particularly, consider smoothness and the reflection sharpness of gained multilayer film, the film thickness after effect film preferably solidifies is 7 μm or thicker, more preferably 8 μm or thicker, and also more preferably 9 μm or thicker.In addition, the film thickness after effect film preferably solidifies is 13 μm or thinner, more preferably 12 μm or thinner, and also more preferably 10 μm or thinner.Such as, the film thickness after this effect film preferably solidifies is 8 μm to 12 μm, and more preferably 9 μm to 11 μm.
operation (3)
In the method for formation multilayer film of the present invention, clear coating composition (C) is coated on the film (being hereafter sometimes referred to as " effect film ") formed by the water-based paint compositions (B) containing effect pigment of formation in above-mentioned operation (2).
Before transparent paint coating composition (C), preferably under the condition of the insufficient solidification of film, preheating, air blast or similar operations are carried out to this effect film.Preheating temperature is preferably 40 ° of C to 100 ° of C, more preferably 50 ° of C to 90 ° of C, and also more preferably 60 ° of C to 80 ° of C.Be preferably 30 seconds to 15 minutes warm up time, more preferably 1 minute to 10 minutes, and also more preferably 2 minutes to 5 minutes.Usually within 30 seconds, aeration operation was carried out to 15 minutes by the air that blows normal temperature at the coating surface of coated article or the air that is heated to 25 to 80 ° of C.
Preferably, before transparent paint coating composition (C), pass through, if needed, pairing effect film carries out preheating, air blast or similar operations, the solids concn of effect film is adjusted to usually 70 quality % to 100 quality %, preferably 80 quality % to 100 quality %, and more preferably 90 quality % to 100 quality %.
As clear coating composition (C), any known thermofixation clear coating composition for Car Body Painting etc. can be used.The example of these thermofixation clear coating compositions comprises all containing linking agent with have the organic solvent type heat curable coating composition of matrix resin of crosslinkable functionality, heat cured water coating composition and powder heat curable coating composition.
The example of the crosslinkable functionality contained in matrix resin comprises carboxyl, hydroxyl, epoxy group(ing) and silanol.The example of matrix resin comprises acrylic resin, vibrin, Synolac, carbamate resins, epoxy resin and fluoro-resin.The example of linking agent comprises polyisocyanate compounds, dead front type polyisocyanate compounds, melamine resin, urea resin, carboxylic compound, carboxylic resin, the resin containing epoxy group(ing) and the compound containing epoxy group(ing).
Example for the preferably combination of the matrix resin/linking agent of clear coating composition (C) is carboxylic resin/containing the resin/melamine resin of the resin of epoxy group(ing), the resin/polyisocyanate compounds of hydroxyl, the resin/dead front type polyisocyanate compounds of hydroxyl and hydroxyl.
Clear coating composition (C) can be single-liquid type coating composition, also can be mulit liquid type coating composition, such as two-pack type carbamate resins coating composition.
If needed, the amount that clear coating composition (C) can not affect clear coating composition transparency comprises tinting pigment, effect pigment, dyestuff etc., also can further suitably containing pigment extender, UV absorption agent, photostabilizer, defoamer, thickening material, sanitas, surface conditioner etc.
Can by known method, such as Airless spraying, aerial spraying or rotary-atomizing application, be coated on the film coated surface that the water-based paint compositions (B) containing effect pigment is formed by clear coating composition (C).Electrostatic can be applied during application.
Film thickness after the solidification that usual transparent paint coating composition (C) obtains is 10 μm to 80 μm, preferably at 15 μm to 60 μm, more preferably 20 μm to 50 μm.
After transparent paint coating composition (C), the interval of under room temperature about 1 minute to 60 minutes can be set as required, or under about 40 ° of C to 80 ° of C, carry out the preheating of about 1 minute to 60 minutes.
operation (4)
In the method for formation multilayer film of the present invention, by heating, uncured painted film, uncured effect film and the uncured transparent coating formed in above-mentioned operation (1) to (3) is solidified simultaneously.
By the ordinary method of the baking film of such as blowing hot-air, infrared heating or ratio-frequency heating, painted film, effect film and transparent coating are solidified.
Heating temperature is preferably 80 ° of C to 180 ° of C, more preferably 100 ° of C to 170 ° of C, and also more preferably 120 ° of C to 160 ° of C.
Be preferably 10 minutes to 60 minutes heat-up time, and more preferably 15 minutes to 40 minutes.Such heating makes three layers of multilayer film, and namely painted film, effect film and transparent coating are solidified simultaneously.
In the method for formation multilayer film of the present invention, seldom form the mixolimnion of water-based colored coating composition (A) and the water-based paint compositions (B) containing effect pigment; Therefore, even if not preheating also can form the multilayer film with excellent smoothness and reflection sharpness.So, the method preferably adopting formation multilayer film of the present invention in-1 curing process is coated with at 3-, wherein in middle layer paint booth application water-based colored coating composition (A), under base layer paint booth not preheating condition, application is containing the water-based paint compositions (B) of effect pigment, and at transparent layer paint booth transparent paint coating composition.In this case, can implement by such as following method I the method forming multilayer film.
method I
By carrying out the method for the formation multilayer film of following operation (1) to (5) successively:
(1) electrodeposition coating material is coated on surface of steel plate, is heating and curing subsequently, form the electrodeposition coating of solidification;
(2) at middle layer paint booth, water-based colored coating composition (A) is coated on the electrodeposition coating of the solidification obtained in operation (1), forms uncured middle film;
(3) the middle film that not preheating is uncured, at base layer paint booth, the water-based paint compositions (B) containing effect pigment is coated on the uncured middle film obtained in operation (2), after forming solidification, film thickness is the uncured matrix film of 7 μm to 13 μm, the described water-based paint compositions (B) containing effect pigment comprises binder ingredients (b1), effect pigment (b2) and hydrophobic solvent (b3), relative to the solids content of the binder ingredients (b1) of 100 mass parts, effect pigment (b2) is 15 mass parts to 30 mass parts, hydrophobic solvent (b3) is 25 mass parts to 60 mass parts, and be 18 quality % to 35 quality % containing the solids concn of the water-based paint compositions (B) of effect pigment,
(4) at transparent layer paint booth, clear coating composition (C) is coated on the uncured matrix film obtained in operation (3), forms uncured transparent coating; And
(5) uncured middle film, uncured matrix film and the uncured transparent coating that are formed respectively in heating process (2) to (4), solidify that this is three-layer coated simultaneously.
Note, above-mentioned paint booth be maintain such as temperature, humidity etc. painting environment condition in specified range to guarantee the facility of homogeneous coating quality.Usually, different paint booths is used according to the type of the class coating material treating application.In addition, sagging, uneven etc. in order to the coating material that prevents from being coated on coated article, sometimes identical coating material is coated on coated article at twice at identical paint booth.Under these circumstances, first time application is called as first stage application, and second time application is called as subordinate phase application.
In method I, after usual application water-based colored coating composition (A) to solidification, the film thickness that obtains is 2 μm to 35 μm, preferably 3 μm to 24 μm, more preferably 4 μm to 19 μm, and also more preferably 5 μm to 16 μm.The film thickness that the water-based paint compositions (B) that usual application contains effect pigment obtains to solidification is 7 μm to 13 μm, preferably 8 μm to 12 μm, and more preferably 9 μm to 11 μm.The film thickness obtained after usual transparent paint coating composition (C) to solidification is 10 μm to 80 μm, preferably 15 μm to 60 μm, and more preferably 20 μm to 50 μm.
The method preferably adopting formation multilayer film of the present invention in-1-curing process is coated with at 3-, wherein application water-based colored coating composition (A) is as the first stage application carried out in base layer paint booth, application containing the water-based paint compositions (B) of effect pigment as the subordinate phase application carried out in base layer paint booth, and in transparent layer paint booth transparent paint coating composition.Under these circumstances, method II such as described below can be used to form film.
method II
By carrying out the method for the formation multilayer film of following operation (1) to (5) successively:
(1) electrodeposition coating material is coated on surface of steel plate, is heating and curing subsequently, form the electrodeposition coating of solidification;
(2) at base layer paint booth, water-based colored coating composition (A) is coated on the electrodeposition coating of the solidification obtained in operation (1), as first stage application, forms the first uncured matrix film;
(3) at the first matrix film that the not preheating of base layer paint booth is uncured, by the water-based paint compositions (B) containing effect pigment, as subordinate phase application, be coated on the first uncured matrix film obtained in operation (2), after forming solidification, film thickness is the second uncured matrix film of 7 μm to 13 μm, the described water-based paint compositions (B) containing effect pigment comprises binder ingredients (b1), effect pigment (b2) and hydrophobic solvent (b3), relative to the solids content of the binder ingredients (b1) of 100 mass parts, effect pigment (b2) is 15 mass parts to 30 mass parts, hydrophobic solvent (b3) is 25 mass parts to 60 mass parts, and be 18 quality % to 35 quality % containing the solids concn of the water-based paint compositions (B) of effect pigment,
(4) at transparent layer paint booth, clear coating composition (C) is coated on the second uncured matrix film obtained in operation (3), forms uncured transparent coating; And
(5) uncured the first matrix film, the second uncured matrix film and the uncured transparent coating that are formed respectively in heating process (2) to (4), solidify that this is three-layer coated simultaneously.
Be at base layer paint booth unlike common 2 stages application, in first stage application and subordinate phase application, use identical coating composition, method II uses different coating compositions in first stage application and subordinate phase application.
More preferably method II in these two kinds of methods above-mentioned and method I and method II, because it does not need middle layer paint booth, thus can reduce the amount of the energy for regulating middle layer paint booth temperature and humidity.
In the method for formation multilayer film of the present invention, seldom form the mixolimnion of water-based colored coating composition (A) and the water-based paint compositions (B) containing effect pigment; Therefore, even if not preheating also can form the multilayer film with excellent smoothness and reflection sharpness.So, in aforesaid method II, preferably adopt the method for formation multilayer film of the present invention, be difficult to add preliminary heating device in described method II, because the application of water-based colored coating composition (A) and the painting containing the water-based paint compositions (B) of effect pigment are contained in identical paint booth carry out.
In the operation (4) of aforesaid method II, the matrix film that can be formed in operation (3) carries out preheating, air blast etc.
In aforesaid method II, after usual application water-based colored coating composition (A) to solidification, the film thickness that obtains is 2 μm to 35 μm, preferably 3 μm to 24 μm, more preferably 4 μm to 19 μm, and also more preferably 5 μm to 16 μm.The film thickness that the water-based paint compositions (B) that usual application contains effect pigment obtains to solidification is 7 μm to 13 μm, preferably 8 μm to 12 μm, and more preferably 9 μm to 11 μm.The film thickness obtained after usual transparent paint coating composition to solidification is 10 μm to 80 μm, preferably 15 μm to 60 μm, and more preferably 20 μm to 50 μm.
The method of formation multilayer film of the present invention makes it possible to be formed the multilayer film with excellent smoothness, reflection sharpness and water-repellancy, even if omit application water-based colored coating composition (A) and to the preheating procedure after the painted film application containing a large amount of solvent contains the water-based paint compositions (B) of effect pigment.The chances are due to application thinly has higher solids concentrations and on painted film, form thin coating film containing the water-based paint compositions (B) of effect pigment containing a large amount of effect pigment for this, and in described thin coating film, resin Composition and effect pigment exist with high-density.This makes solvent contained in painted film be difficult in entrance effect film.Further, because the water-based paint compositions (B) containing effect pigment is containing relatively large hydrophobic solvent (b3), the shipwreck contained by painted film is with in entrance effect film.Therefore, it is possible to suppress water-based colored coating composition (A) and form mixolimnion containing the water-based paint compositions (B) of effect pigment.
(II) with application water-based colored coating composition (A) after 30 seconds solids content and viscosity for feature embodiment
As preferred embodiment, the invention provides the method for the formation multilayer film described in following item 1B and 2B.
Item 1B: the method forming multilayer film, carries out following operation (1) successively to (4):
(1) application water-based colored coating composition (A) on coated article, forms uncured painted film;
(2) not preheating, to the solids content of the uncured painted film application formed in the operation (1) relative to the binder ingredients (b1) of 100 mass parts, comprise the water-based paint compositions (B) containing effect pigment of the effect pigment of 15 mass parts to 30 mass parts, after forming solidification, film thickness is the uncured effect film of 7 μm to 13 μm;
(3), after the effect film that preheating is uncured, transparent paint coating composition (c) on the uncured effect film obtained in operation (2), forms uncured transparent coating; And
(4) uncured painted film, uncured effect film and the uncured transparent coating that are formed respectively in operation (1) to (3) is heated, three-layer coated to solidify this simultaneously;
When 20 ° of C temperature and 65% humidity under application water-based colored coating composition (A) thus after making solidification, the thickness of film is 20 μm time, water-based colored coating composition (A) solids content of 30 seconds after its application is 45% to 65%, and after its application 30 seconds at 23 ° of C, 0.1sec -1shearing rate under the viscosity that measures be 50,000mPaS to 500,000mPaS.
Item 2B: the method for the formation multilayer film as described in item IB, a part for the resin Composition as binder ingredients of wherein said water-based colored coating composition (A) is aqueous urethane resin.
The coated article addressed in " coated article " item in above-mentioned first embodiment still can be used as the coated article in this embodiment.Also can use the coated article forming film thereon, the film of formation is included in the bottom film that above-mentioned coated article is formed.In multiple different spendable raw material, particularly preferably use the coated article forming film thereon.
The bottom film formed hides the surface of coated article, gives erosion resistance and rust resistance, or improves the adhesive power between film that coated article and following water-based colored coating composition (A) formed.Can then solidify primer composition by application and form bottom film.Raw material for primer composition is not particularly limited, and such as, when coated article be metal or surperficial treated metal time, can cation electric deposition paint composition be used.
If the example of spendable cation electric deposition paint composition comprises the known cation electric deposition paint composition that also can add the acquisition of other additive by such as adding linking agent, multiple pigment and needs in the aqueous solution or dispersion liquid of cationic polymeric compounds.The example of cationic polymeric compounds comprise that acrylic resin or epoxy resin by amino being introduced the crosslinkable functionality containing such as hydroxyl obtain those.Gained cationic polymers organic acid or mineral acid neutralization, to dissolve or to disperse this cationic polymeric compounds thus the aqueous solution of acquisition cationic polymeric compounds or dispersion liquid.The example of linking agent comprises dead front type polyisocyanate compounds and alicyclic epoxide compound.
By such as coated article being immersed in cation electric deposition paint composition bath (preferably its solids content is 10 to 35 quality %) as negative electrode, and electric current application cation electric deposition paint composition can be applied under normal conditions subsequently.Film thickness after solidification is preferably about 10 μm to 40 μm.At about 130 ° of C to 200 ° of C after being washed by this film, preferably heat solidification in about 10 minutes to 40 minutes under about 150 ° of C to 180 ° of C.
In the present invention, coated article can be used as by by resistance to coating composition painting of bursting apart is contained in the film that the film of cation electric deposition paint composition formation obtains.On multilayer film, the resistance to coating composition that bursts apart of application is to prevent film from coming off due to the shock caused by the stone with its collision etc., and suppresses the deterioration of film erosion resistance and steel plate and analogue owing to clashing into the progress of the corrosion caused of peeling.The example of the known resistance to coating composition that bursts apart comprises those and contains polyolefin resin or carbamate resins and form the coating composition of component (in this manual, medium form component be equal to binder ingredients) and the coating composition containing synthetic latex and similar particle as medium.In the present invention, the film being coated with the known resistance to coating composition that bursts apart can be used as coated article.
Can by the known method such as resistance to coating composition that bursts apart of aerial spraying, Airless spraying and electrostatic spraying application.Film thickness is preferably about 5 μm to 200 μm, and more preferably from about 40 μm to 100 μm.Heating condition depends on binder ingredients contained in coating composition.Heating temperature is preferably about 20 ° of C to 200 ° of C, and heat-up time is preferably about 10 minutes to 60 minutes.
In the operation (1) of the method for formation multilayer film of the present invention, water-based colored coating composition (A) is coated with and is contained on coated article.Water-based colored coating composition (A) of the present invention hides coated article color and the clinging power improved between film that coated article and following water-based colored coating composition (A) formed thus make the coating composition of the enough waterproof of gained multilayer film and application.
In the present embodiment, by resinous component (i.e. binder ingredients) and tinting pigment but not water-based colored coating composition (A) of the present invention can be used as containing the water-based paint compositions of effect pigment.
Be in the embodiment of feature with the solids content of application water-based colored coating composition (A) after 30 seconds and viscosity, those known resins being usually used as binder ingredients in the coating composition can be used as binder ingredientss of water-based colored coating composition (A).The example of these resins comprises acrylic resin, vibrin, Synolac and carbamate resins.In the present invention, the resin containing the such as crosslinkable functionality of hydroxyl, carboxyl or epoxy group(ing) is preferably used.The resin addressed in the explanation of the first embodiment also can be used in this embodiment.
Water-based colored coating composition (A) can contain solidifying agent further.When water-based colored coating composition (A) is containing solidifying agent, usually will containing the crosslinkable functionality of such as hydroxyl, carboxyl or epoxy group(ing), and can by with solidifying agent react form cured coating film resin (matrix resin) as above-mentioned resin.The resin solid content of water-based colored coating composition (A) of the present invention is the total mass of above-mentioned resin and solidifying agent solid ingredient.The resin addressed in the explanation of the first embodiment also can be used in this embodiment.
The example of above-mentioned resin comprises acrylic resin, vibrin and Synolac.Wherein, matrix resin is preferably the resin of hydroxyl, more preferably the acrylic resin of hydroxyl and/or the vibrin of hydroxyl.Further preferably by the vibrin coupling of the acrylic resin of hydroxyl and hydroxyl, to improve the outward appearance after the completing of film and water-repellancy.When these resin couplings, relative to the total amount of the acrylic resin of hydroxyl and the vibrin of hydroxyl, the content of the acrylic resin of hydroxyl is preferably about 20 quality % to 80 quality %, and more preferably from about 30 quality % to 70 quality %; And the content of the vibrin of hydroxyl is preferably about 80 quality % to 20 quality %, and more preferably from about 70 quality % to 30 quality %.
When using the resin containing carboxyl or similar acidic-group, the acid number of resin is preferably about 5mg KOH/g to 150mg KOH/g, more preferably from about 10mg KOH/g to 100mgKOH/g, and more preferably from about 15mg KOH/g to 80mg KOH/g.When using the resin of hydroxyl, the hydroxyl value of resin is preferably about 1mg KOH/g to 200mg KOH/g, more preferably from about 2mg KOH/g to 180mg KOH/g, and also more preferably from about 5mg KOH/g to 170mgKOH/g.
In the present embodiment, when 20 ° of C temperature, 65% humidity under application water-based colored coating composition (A) thickness that makes to solidify rear gained film be 20 μm time, the solids content of water-based colored coating composition (A) application after 30 seconds is 45% to 65%, and at 23 ° of C, 0.1sec -1shearing rate under the viscosity of application after 30 seconds that measures be 50,000mPaS to 500,000mPaS.In this embodiment, water-based colored coating composition (A) of the present invention preferably contains aqueous urethane resin as binder ingredients, to prevent when the water-based paint compositions (B) containing effect pigment being coated on water-based colored coating composition (A) when non-preheating, water-based colored coating composition (A) and the water-based paint compositions (B) containing effect pigment form mixolimnion.
Be not particularly limited aqueous urethane resin, usually known aqueous urethane resin all can use.Preferred use median size is 0.01 μm to 1 μm, and the more preferably granule type emulsion of 0.1 μm to 0.5 μm.
In the present invention, in order to make film have excellent stability in storage and water-repellancy, the acid number of aqueous urethane resin is preferably 5mg KOH/g to 100mg KOH/g, and more preferably 10mg KOH/g to 70mg KOH/g.
In the present invention, aqueous urethane resin can be obtained by being such as scattered in water by the carbamate prepolymer that the reaction of polymeric polyisocyanate, polyvalent alcohol and carboxylic glycol is formed.
The example of polymeric polyisocyanate comprises hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, dimer acid diisocyanate, lysinediisocyanate and similar aliphatic diisocyanate compound, the biuret form adducts of these diisocyanate cpds or the ring-like adducts of isocyanide urea (isocyanuric ring-type adduct), isophorone diisocyanate, 4,4 '-methylene-bis (cyclohexyl isocyanate), methylcyclohexane-2,4-(or-2,6-) vulcabond, 1,3-(or Isosorbide-5-Nitrae-) two (isocyanatomethyl) hexanaphthene, Isosorbide-5-Nitrae-cyclohexyl diisocyanate, 1,3-pentamethylene vulcabond, 1,2-cyclohexyl diisocyanate and similar alicyclic diisocyanate compound, the biuret form adducts of these vulcabond or the ring-like adducts of isocyanide urea, eylylene diisocyanate, between eylylene diisocyanate, tetramethyl xylylen vulcabond, toluylene diisocya-nate, 4, 4'-diphenylmethanediisocyanate, 1, 5-naphthalene diisocyanate, 1, 4-naphthalene diisocyanate, 4, 4'-toluidine diisocyanate, 4, 4'-diphenyl ether diisocyanate, (or to) phenylene vulcabond, 4, 4'-biphenyl diisocyanate, 3, 3'-dimethyl-4, 4'-biphenyl diisocyanate, two (4-isocyanatophenyl) sulfone, isopropylidene two (4-phenyl isocyanate) and similar aromatic diisocyanate compounds, the biuret form adducts of these diisocyanate cpds or the ring-like adducts of isocyanide urea, triphenyl methane-4,4', 4 "-triisocyanate, 1,3, 5-tri-isocyanato benzene, 2,4,6-tri-isocyanato toluene, 4,4'-dimethyl diphenylmethanes-2, 2', 5,5'-tetraisocyanate and per molecule have the similar polyisocyanate compounds of at least three isocyanate group, the biuret form adducts of these polyisocyanate compounds or the ring-like adducts of isocyanide urea, the urethane adducts obtained is reacted with the ratio that isocyanate group is excessive relative to polyol hydroxyls by making the polyvalent alcohol of such as ethylene glycol, propylene glycol, BDO, dimethylol propionic acid, polyalkylene glycol, TriMethylolPropane(TMP) or hexanetriol and polyisocyanate compounds, the biuret form adducts of these urethane adductss or the ring-like adducts of isocyanide urea.
The example of polyvalent alcohol comprises the polyvalent alcohol that those weight-average molecular weight are 200 to 10,000.Its specific examples comprises polyoxyethylene glycol, polypropylene glycol, polyvinyl-propenyl (block or random) glycol, polytetramethylene ether diol, polyhexamethylene ether glycol, poly-eight methylene ether glycol and similar polyether glycol, dicarboxylic acid (hexanodioic acid, succsinic acid, sebacic acid, pentanedioic acid, toxilic acid, fumaric acid, phthalic acid etc.) and glycol (ethylene glycol, propylene glycol, 1, 4-butyleneglycol, 1, 6-hexylene glycol, 3-methyl isophthalic acid, 5-pentanediol, neopentyl glycol, hydroxymethyl-cyclohexane etc.) polycondensation obtain polyvalent alcohol, such as polyethylene glycol adipate, poly adipate succinic acid ester, polyhexamethylene adipic acid ester, poly-neopentyl adipate, poly-3-methyl amyl adipic acid ester, polyoxyethylene glycol/butyleneglycol adipic acid ester (polyethylene/butylene adipate), poly-neo-pentyl/hexyl adipic acid ester and similar polyester polyol, polycaprolactone polyol, poly-3-methylpent lactone polyols, polycarbonate polyol, ethylene glycol, glycol ether, triglycol, 1,2-propylene glycol, 1,4-butyleneglycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, ethohexadiol, Tricyclodecane Dimethanol, Hydrogenated Bisphenol A, cyclohexanedimethanol, 1,6-hexylene glycol and similar low molecular weight diols compound.These polyvalent alcohols can be used alone, or two or more couplings.
The example of carboxylic glycol comprises dihydroxymethyl acetic acid, dimethylol propionic acid, dimethylolpropionic acid, dimethylol propionic acid and dimethylolpropionic acid.
In the present invention, basic cpd neutralized aqueous carbamate resins can be used.The example of basic cpd comprises monoethanolamine, ethamine, dimethylamine, triethylamine, propylamine, dipropyl amine, Isopropylamine, Diisopropylamine, trolamine, butylamine, dibutylamine, 2 ethyl hexylamine, quadrol, propylene diamine, Mono Methyl Ethanol Amine, dimethylethanolamine, diethylethanolamine, 2-amino-2-methyl propyl alcohol, diethanolamine, morpholine and similar water-soluble amino compound and ammonia.The consumption of neutralizing agent is generally every equivalent carboxyl 0.5 equivalent to 2.0 equivalent in aqueous urethane resin, preferably 0.7 equivalent to 1.3 equivalent.
In order to the viscosity and solids content that adjust coating process composition film after 30 seconds fall within the scope of following regulation, and make gained multilayer film have excellent water-repellancy, relative to the total amount of the resin as one of tackiness agent of water-based colored coating composition (A), the amount of aqueous urethane resin is preferably about 20 quality % to 80 quality % in water-based colored coating composition (A) of the present invention, and more preferably from about 30 quality % to 70 quality %.
Solidifying agent solidifies water-based colored coating composition (A) of the present invention by reacting with hydroxyl, carboxyl, epoxy group(ing) and similar crosslinkable functionality.The example of solidifying agent comprise aminoresin, polyisocyanate compounds, dead front type polyisocyanate compounds, the compound containing epoxy group(ing), carboxylic compound, carbodiimide compound, containing hydrazides compound and containing Urea,amino-compound.Wherein preferably can with the aminoresin of hydroxyl reaction, can with the compound of the polyisocyanate compounds of carboxyl reaction, dead front type polyisocyanate compounds and carbodiimide.Wherein, particularly preferably aminoresin.These solidifying agent can be used alone or two or more couplings.
Spendable aminoresin comprises the part or all of methylolated aminoresin that amino group and aldehyde component reaction obtain.The example of these amino groups comprises trimeric cyanamide, urea, benzoguanamine, methyl guanamines, steroguanamine, spiroguanamine and Dyhard RU 100.The example of these aldehyde components comprises formaldehyde, paraformaldehyde, acetaldehyde and phenyl aldehyde.
The resin by suitable alcohol moiety or all methylol acquisitions of the aminoresin of etherfied methylol can also be used.The example that can be used for the alcohol of etherification reaction comprises methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, 2-ethyl butanol and 2-Ethylhexyl Alcohol.
Preferably melamine resin is used as aminoresin.Particularly, preferably by the methyl-etherified melamine resin part or all of methylol etherificate of part or all of methylolated melamine resin obtained with methyl alcohol; By the fourth etherify melamine resin part or all of methylol etherificate of part or all of methylolated melamine resin obtained with butanols; And by using methyl alcohol and butanols by the melamine resin of the methyl-butvl mixture etherificate of the part or all of methylol etherificate acquisition of part or all of methylolated melamine resin.The wherein melamine resin of particularly preferably methyl-butvl mixture etherificate.
With regard to the water-repellancy of gained film, the weight-average molecular weight of melamine resin is preferably 400 to 6,000, and more preferably 500 to 4,000, and also more preferably 600 to 3,000.
Commercially available melamine resin can be used.The example of commercially available prod comprises Cymel202, Cymel203, Cymel238, Cymel251, Cymel303, Cymel323, Cymel324, Cymel325, Cymel327, Cymel350, Cymel385, Cymel1156, Cymel1158, Cymel1116 and Cymel1130 (Nihon Cytec Industries Inc. produces), U-VAN120, U-VAN20HS, U-VAN20SE60, U-VAN2021, U-VAN2028 and U-VAN28-60 (Mitsui Chemicals, Inc. produce).
When melamine resin is used as solidifying agent, tosic acid, Witco 1298 Soft Acid, dinonylnaphthalene sulfonic acid and similar sulfonic acid; Mono phosphoric acid ester butyl ester, dibutyl phosphate, list-ethylhexyl dihydrogen phosphate, two-ethylhexyl dihydrogen phosphate and similar alkyl phosphate; And these acid can be used as catalyzer with the salt of aminocompound.
Polyisocyanate compounds per molecule has at least two isocyanate group.The example comprises hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, dimer acid diisocyanate, lysinediisocyanate and similar aliphatic diisocyanate compound; Hydrogenation eylylene diisocyanate, cyclohexyl diisocyanate (cyclohexylene diisocyanate), isophorone diisocyanate and similar alicyclic diisocyanate compound; Toluylene diisocya-nate, phenylene vulcabond, 4,4'-diphenylmethanediisocyanates, eylylene diisocyanate, tetramethyl xylylen vulcabond, naphthalene diisocyanate and similar aromatic diisocyanate compounds; The organic polyisocyanates compound of trivalent or more high price, such as 2-isocyanatoethyl-2, the diisocyanate based capronate of 6-, 3-isocyanatomethyl-1,6-hexamethylene diisocyanate, 4-isocyanatomethyl-1,8-eight methylene diisocyanate (being commonly referred to triamino-nonane triisocyanate); The dipolymer of these polyisocyanate compounds or trimer; And these polyisocyanate compounds and polyvalent alcohol, low-molecular-weight vibrin or water carry out urethane and react the prepolymer obtained under the excessive existent condition of isocyanate group.
When polyisocyanate compounds is used as solidifying agent, the example of spendable catalyzer comprises stannous octoate, dibutyltin diacetate, dibutyl two isocaprylic acid tin, dibutyl tin laurate, dibutyltin diacetate, dioctyl two isocaprylic acid tin, Dibutyltin oxide, dioctyl tin oxide, dibutyl tin soap, 2 ethyl hexanoic acid lead, zinc octoate, zinc naphthenate, fatty acid zinc compound, cobalt naphthenate, calcium octoate, copper naphthenate, four (2-ethylhexyl) titanic acid ester and similar organometallic compounds; Tertiary amine; Phosphate cpd etc.These compounds can be used alone or two or more couplings.
Can by obtaining dead front type polyisocyanate compounds by the isocyanate group of blocking agent polyisocyanate compounds.Spendable encapsulant comprises oxime compound, phenolic compound, alkylol cpd, lactam compound, mercaptan compound and analogue.
The example of the compound of carbodiimide comprise by the isocyanate group of polyisocyanate compounds is carried out carbonic acid gas removes that reaction obtains those.The compound of commercially available carbodiimide comprises such as Carbodilite V-02, Carbodilite V-02-L2, Carbodilite V-04, Carbodilite E-01 and Carbodilite E-02 (Nisshinbo Industries, Inc. produce).
Water-based colored coating composition (A) of the present invention is containing the colored pigment in order to cover coated article color and adjustment multilayer film hue and luminance.Be not particularly limited for colored pigment, its concrete example comprises mineral dye, such as transparent iron oxide pigments, titan yellow and similar complex oxide pigment; And pigment dyestuff, such as azo pigment, quinacridone-type pigments, diketopyrrolopyrroles pigment, perylene class pigment, purple cyclic ketones class pigment, benzoglyoxaline ketone pigment, isoindoline class pigment, isoindoline ketone pigment, azo metal inner complex pigment, phthalocyanine pigment, indanthrone class pigment, bisoxazines class pigment, reduction class pigment (threne-basedpigment) and indigo class pigment; And titanium oxide pigment and charcoal blacks.Can be used alone or two or more couplings by one or more pigment of unrestricted choice.In the present invention, preferably use titanium oxide pigment to cover the color of coated article.
Titanium oxide pigment is widely used as white pigment owing to having high refractive index.Titanium oxide pigment is divided into two types according to crystallographic system, i.e. rutile-type and anatase titanium dioxide.The titanium dioxide of this two type all can be used for the present invention; But, consider from weathering resistance angle, preferably use rutile titanium dioxide.In addition, in order to improve dispersibility and weathering resistance, the surface of the mineral compound process titanium dioxide of such as silicon-dioxide, zirconium white or aluminum oxide can be used.In the present invention, in order to reach the promising result of covering coated article color, the average initial particle of titanium oxide pigment is preferably 100nm to 400nm, and more preferably 200nm to 300nm.
When titanium oxide pigment being used as colored pigment in water-based colored coating composition (A), outward appearance after having considered, relative to the resin solid content of 100 mass parts, the content of titanium oxide pigment is preferably 30 mass parts to 200 mass parts, and more preferably 50 mass parts to 120 mass parts.
In order to adjust the brightness of multilayer film, water-based colored coating composition (A) can containing one or more colored pigments except titanium oxide pigment.In the case, in order to multilayer film obtains the brightness expected, relative to the resin solid content of 100 mass parts, the content of this pigment is preferably 0.1 mass parts to 50 mass parts, and more preferably 0.5 mass parts to 20 mass parts.
In addition, if needed, water-based colored coating composition (A) can contain water, organic solvent and similar solvent; Pigment dispersing agent, antisettling agent, curing catalyst, defoamer, antioxidant, UV absorption agent and similar additive; Pigment extender etc.Can by said components being mixed and disperseing preparation water-based colored coating composition (A).During application, the solids content of coating composition is preferably adjusted to 30 quality % to 70 quality % by (before namely solidifying), preferably to 40 quality % to 60 quality %, it is 300mPas to 2,500mPas (revolution: 6) by the viscosity that Brookfield viscometer is measured.
In operation of the present invention (1), by electrostatic coating, aerial spraying, Airless spraying etc., water-based colored coating composition (A) is coated on coated article.In order to cover the color of coated article or make gained film have the outward appearance after completing of excellence, the coating thickness after preferred consolidation is 10 μm to 30 μm, and more preferably 15 μm to 25 μm.
In operation of the present invention (2), after application water-based colored coating composition (A), not preheating is about to be coated on the uncured painted film that obtains in operation (1) (in this manual containing the water-based paint compositions (B) of effect pigment, uncured painted film can be called as the first matrix film), form the second matrix film.In the case, mixolimnion is formed in order to prevent the first matrix film and the second matrix film, and improve the brightness of gained multilayer film, preferably water-based colored coating composition (A) of the present invention painting being filled to the rear film thickness of solidification is 20 μm, and the solids content of its application after 30 seconds is 45% to 65%.In addition, when 20 ° of C temperature and 65% humidity under application water-based colored coating composition (A) of the present invention time, its application after 30 seconds at 23 ° of C and 0.1sec -1shearing rate under the viscosity that measures be preferably 50,000mPas to 500,000mPas.
By wiping the part film of coating process composition after 30 seconds off and measure coating NV (non-VOC) value after dry 1 hour under 110 ° of C, obtain the solids content of coating process composition after 30 seconds.More specifically, the coating composition heating 1 ± 0.1g under 110 ° of C detects heating residual quantity (i.e. non-volatile contents) after 1 hour, and by the weight (the scope of 1 ± 0.1g in) of this heating residual quantity divided by dry front coating composition.
In this manual, the viscosity of after application first matrix film 30 seconds is defined in the following manner.Use the Cartridge Bell System (trade(brand)name of the bell coating equipment of rotary-atomizing and ABB, ABB K.K. produces) single coating of application water-based colored coating composition (A), the film thickness after solidifying is made to become 20 μm, condition is as follows: clock diameter 77mm, clock rotating speed: 25,000rpm, shaping air speed (shaping air flow rate): 700NL/min, the voltage applied :-60kV, temperature: 23 ° of C and humidity: 75%.Application water-based colored coating composition (A), after 30 seconds, is wiped off with spatula etc. and collects part film.When shearing rate is by 10,000sec -1be changed to 0.0001sec -1time with viscosimetric analysis device at 23 ° of C, 0.1sec -1shearing rate under measure the viscosity of the film of collection.The viscosity of mensuration like this is defined as the viscosity of after application 30 seconds.One of example of viscosimetric analysis device is HAAKE RheoStress RS150 (trade(brand)name, HAAKE produces).It should be noted that, the unit NL/min of shaping air speed is generally used in the measurement carried out with the area meter measuring air-flow, wherein by the volume of (0 ° of C, 1atm and normal atmosphere) under being converted into standard state by the shaping airflows volume of pipe in 1 minute.
By aqueous urethane resin is used as resin Composition, the solids content of rheology control agent or adjustment coating composition can be added to control application water-based colored coating composition (A) viscosity of latter 30 seconds.
The example of rheology control agent comprises the inorganic thickening agents such as silicate, metal silicate, montmorillonite, organic montmorillonite, colloidal alumina; Sodium polyacrylate, polyacrylic acid/(methyl) acrylate copolymer and similar agent for polyacrylic acid thickening; Carbamate associative thickeners, its per molecule has amino-formate bond and polyether chain, and is bonded to each other by amino-formate bond in water medium and effectively shows thickening effect.(example of commercially available carbamate associative thickener comprises UH-814N, UH-462, UH-420, UH-472 and UH-540, and Asahi DenkaKogyo K.K. produces; And SN Thickener612, SN Thickener621N, SNThickener625N and SN Thickener627N (San Nopco Ltd. produces); Carboxymethyl cellulose, methylcellulose gum, Natvosol and similar derivatived cellulose thickening material; Casein, sodium-caseinate, ammonium caseinate and similar albumen thickening material; Sodiun alginate and similar Lalgine thickening material; Polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl benzyl ether copolymer and similar polyethylene kind thickening material; The product that pluronic polyethers (pluronic polyether), polyethers dialkyl, polyethers dialkyl ether, polyethers are epoxide modified and similar polyethers thickening material; The partial ester of the multipolymer of vinyl methyl ether and maleic anhydride and similar copolymer-maleic anhydride thickening material; Polymeric amide amine salt and similar polyamide-based thickening material.Wherein, the thickening material that optimization polypropylene Acrylic associative thickener or carbamate associate, the thickening material of particularly preferably carbamate association.These rheology control agents can be used alone or two or more couplings.
In order to obtain outward appearance and water-repellancy after the completing of the multilayer film of expectation, in operation of the present invention (2), be preferably 45% to 65% in the application solids content (non-volatile wet film) of the first matrix film, and at 23 ° of C, 0.1sec -1shearing rate under the application viscosity that measures carry out the application of the water-based paint compositions (B) containing effect pigment when being 50,000mPas to 500,000mPas.Can by with measure the value determination application solids content and viscosity that the application mode that after 30 seconds, viscosity is identical with solids content measures.
In operation of the present invention (2), mixolimnion is formed in order to prevent the first matrix film and the second matrix film, and the clinging power simultaneously strengthened between the first matrix film and the second matrix film, after application first water-based matrix coating composition, preferably at room temperature solidify about 1 minute to 10 minutes, and more preferably 2.5 minutes to 6 minutes.
In the present embodiment, be containing effect pigment containing the water-based paint compositions (B) of effect pigment and not preheating first matrix film and the coating composition be coated on the first uncured matrix film.In the water-based paint compositions (B) containing effect pigment, consider outward appearance and the clinging power between the first matrix film and the second matrix film after the completing of multilayer film, relative to the resin Composition of 100 mass parts, the content of effect pigment is preferably 15 mass parts to 50 mass parts, and more preferably 18 mass parts to 30 mass parts.The example of spendable effect pigment with address in above-mentioned item (1) identical, and wherein preferred laminar effect pigment.The example of flake effect pigment comprises platelet like metal pigments, such as aluminium, copper, nickelalloy and stainless steel, by the platelet like metal pigments that metal oxide covers, adhere to the platelet like metal pigments of tinting pigment to its surface chemistry, formed the laminar aluminium pigment of alumina layer by induced oxidation reduction reaction on its surface, the ferriferous oxide thin flaky pigment of dissolved aluminum, glass flake pigments, by the glass flake pigments that metal or metal oxide cover, the glass flake pigments of colored pigment is adsorbed in its surface chemistry, by the reflective interference pigments, mica (interference micapigment) that titanium dioxide covers, the reduction pigments, mica that reflective interference pigments, mica of reducing obtains, adsorbs in its surface chemistry coloured pigments, mica that Color paint or its surface covered by ferriferous oxide, by the graphite pigment that titanium dioxide covers, the silicon-dioxide thin slice covered by titanium dioxide or alumina wafer pigment, ferriferous oxide flaky pigment, holographic pigment, synthetic mica pigment, spiral container sterol liquid crystal polymer pigments and bismuth oxychloride pigments.
In the present invention, the water-based paint compositions (B) containing effect pigment can further containing being suitably selected from those the colored pigment mentioned as the spendable example for above-mentioned water-based colored coating composition (A).In the present invention, consider brightness and the water-repellancy of gained multilayer film, relative to the resin solid content of 100 mass parts in hereinafter described coating composition, the amount of colored pigment is preferably 10 mass parts to 50 mass parts, and more preferably 12 mass parts to 25 mass parts.
In the present invention, containing the water-based paint compositions (B) of effect pigment can use can use in water-based colored coating composition (A) those as binder ingredients, resin and solidifying agent.In the water-based paint compositions (B) containing effect pigment of the present invention, preferably by the vibrin coupling of the acrylic resin of hydroxyl and hydroxyl, and add solidifying agent further to obtain the multilayer film with outward appearance after excellent completing.
In addition, containing effect pigment water-based paint compositions (B) if need can contain water, organic solvent and similar solvent; Pigment dispersing agent, antisettling agent, curing catalysts, defoamer, antioxidant, UV absorption agent and similar additive; Pigment extender etc.Can by said components being mixed and disperseing preparation second matrix coating composition.During application, the solids content of the water-based paint compositions (B) containing effect pigment is preferably adjusted to 30 quality % to 70 quality % by (before namely solidifying), and preferred 40 quality % to 60 quality %, with Brookfield viscometer measure viscosity be 300mPas to 2,500mPas (revolution: 6).
In the present embodiment, namely use application after 30 seconds viscosity fall into the embodiment of the water-based colored coating composition (A) of above-mentioned scope, the content of hydrophobic solvent (b3) is not particularly limited.Content preferably 25 mass parts to 60 mass parts of hydrophobic solvent (b3), more preferably 30 mass parts to 50 mass parts, and more preferably 35 mass parts to 45 mass parts.
In operation of the present invention (2), in order to obtain the multilayer film with outward appearance and water-repellancy after excellent completing, preferred application, containing the water-based paint compositions (B) of effect pigment, makes the thickness after gained curing of coating be 7 μm to 13 μm.
In the present embodiment, after application contains the water-based paint compositions (B) of effect pigment, in order to prevent the first matrix film and the second matrix film from occurring breaking or similar defect, in operation (3), carry out the top layer clear coating composition that after preheating (tentatively heating), application is following again.The temperature of preheating is preferably 40 ° of C to 100 ° of C, more preferably 50 ° of C to 90 ° of C, and also more preferably 60 ° of C to 80 ° of C.Be preferably 30 seconds to 15 minutes warm up time, more preferably 1 minute to 10 minutes, and also more preferably 2 minutes to 5 minutes.
In operation (3), after preheating, one deck of application top layer clear coating composition, two-layer or multilayer, form transparent coating.
The top layer clear coating composition used in the method for formation multilayer film of the present invention contains resin Composition and solvent as main ingredient, if needed also containing other additives for coating composition.Top layer clear coating composition is the liquid coating composition that can form coloured or transparent film.
The top layer clear coating composition used in the present invention does not limit, and can use multiple known coating composition.The example of spendable coating composition comprises the coating composition of the aqueous or powdery containing matrix resin and linking agent.The example of matrix resin comprises acrylic resin, vibrin, Synolac, fluoro-resin, carbamate resins and containing silicone resin containing hydroxyl, carboxyl, silicone hydroxyl, epoxy group(ing) and similar crosslinkable functionality.The example of linking agent comprises melamine resin, urea resin, polyisocyanate compounds, dead front type polyisocyanate compounds, epoxy compounds or the resin that can react with matrix resin, carboxylic compound or resin, acid anhydrides and contains compound or the resin of organoalkoxysilane.If need in addition to add water, organic solvent and similar solvent; Curing catalysts, defoamer, rheology control agent, antioxidant, coating materials and similar additive.
The amount that top layer clear coating composition can not weaken clear coating composition transparency contains colored pigment.Spendable colored pigment comprises usually the known pigment used in ink or coating composition; And these pigment can be used alone or two or more couplings.Suitably can select the amount of the colored pigment added.Relative to the resin solid content of the top layer clear coating composition of 100 mass parts, the amount of colored pigment is generally 30 mass parts or less, and preferred 0.01 mass parts to 5 mass parts.
The application top layer clear coating compositions such as electrostatic spraying, aerial spraying, Airless spraying can be passed through.Thickness after its solidification is preferably 5 μm to 40 μm.
In operation of the present invention (4), in operation (1) to (3), the three-layer coated of acquisition is solidified by heating simultaneously.After application top layer clear coating composition, if needed, the interval that can at room temperature have an appointment 1 minute to 60 minutes, or the preheating carrying out about 1 minute to 60 minutes under about 40 ° of C to 80 ° of C.
Three-layer coated being heating and curing can be carried out by known heating means.Such as, the method described in the above-described first embodiment can be used.
(III) wherein water-based colored coating composition (A) comprises specific carbamate resins breast the embodiment of liquid
Another preferred embodiment in, the invention provides the method for the formation multilayer film according to following item 1C to 3C:
Item 1C: the method forming multilayer film, comprises following operation (1) to (4):
(1) application water-based colored coating composition (A) on coated article, forms uncured painted film,
This water-based colored coating composition (A) comprises binder ingredients (a1) and pigment (a2),
This binder ingredients (a1) comprises use polyisocyanate component and polyol component is the carbamate resins emulsion (a1-1 (c)) of 2,000 to 50,000 as weight-average molecular weight prepared by starting raw material,
This polyisocyanate component comprises alicyclic diisocyanate, and
Relative to polyol component total amount, this polyol component comprises the polycarbonate diol of 50 quality % or more;
(2) the painted film that not preheating is uncured, on the uncured painted film formed in operation (1), application comprises the water-based paint compositions (B) containing effect pigment of binder ingredients (b1), effect pigment (b2) and hydrophobic solvent (b3), after forming solidification, film thickness is the uncured effect film of 7 μm to 13 μm, wherein, relative to the solids content of the binder ingredients (b1) of 100 mass parts, effect pigment (b2) is 15 mass parts to 30 mass parts, and hydrophobic solvent (b3) is 25 mass parts to 60 mass parts;
(3) transparent paint coating composition (C) on the uncured effect film formed in operation (2), forms uncured transparent coating; And
(4) uncured painted film, uncured effect film and the uncured transparent coating that are formed respectively in heating process (1) to (3), solidify that this is three-layer coated simultaneously.
Item 2C: the method for the formation multilayer film according to item 1C, wherein polycarbonate diol obtains by making diol component and the reaction of carbonyl agent, relative to diol component total amount, this diol component comprises the glycol with 6 or more carbon atoms of 90 quality % or more, and the glycol with 6 or more carbon atoms comprises the alicyclic diol containing ring alkylidene group with 6 or more carbon atoms.
Item 3C: the method for the formation multilayer film according to item 1C or 2C, wherein pigment (a2) comprises titanium dioxide and/or barium sulfate, and the solids content of binder ingredients (a1) relative to 100 mass parts, the total content of titanium dioxide and barium sulfate is 50 mass parts to 150 mass parts.
The coated article addressed in " coated article " item in the above-described first embodiment also can be used in this embodiment.
water-based colored coating composition (A)
The water-based colored coating composition (A) being filled to coated article to be coated can be, such as, comprises binder ingredients (a1), pigment (a2) and optionally for the coating composition of the additive etc. of coating composition.
binder ingredients (a1)
It is 2 that binder ingredients (a1) comprises as its weight-average molecular weight at least partially, 000 to 50, the carbamate resins emulsion (a1-1 (c)) of 000, it is prepared by initial feed by the polyol component of the polyisocyanate component containing alicyclic diisocyanate and the polycarbonate diol containing 50 quality % or more.If need to use the known film-forming resin being used as coating composition binder ingredients as binder ingredients (a1).Non-crosslinked type resin and crosslinked resin all can use.
Carbamate resins emulsion (a1-1 (c)) has following feature: prepare emulsion by making polyisocyanate component and polyol component react; Polyisocyanate component contains alicyclic diisocyanate; And relative to polyol component total amount, polyol component contains the polycarbonate diol of 50 quality % or more.
The example of polyisocyanate component comprises alicyclic diisocyanate as main ingredient and other polymeric polyisocyanate.
The example of alicyclic diisocyanate comprises isophorone diisocyanate, dicyclohexyl methyl hydride-4,4 '-vulcabond, trans Isosorbide-5-Nitrae-cyclohexyl diisocyanate and norcamphane vulcabond.Consider the anti-organic solvent swelling property improving gained film, wherein particularly preferably isophorone diisocyanate and dicyclohexyl methyl hydride-4,4'-vulcabond as alicyclic diisocyanate.
Consider chipping resistance, in polyisocyanate component, the content (quality %) of aliphatic diisocyanate is preferably 50% to 100%, and more preferably 70% to 100%.
The example of other polymeric polyisocyanate is the vulcabond except alicyclic diisocyanate, and per molecule has the polymeric polyisocyanate of three or more isocyanate group.
The example of the vulcabond except alicyclic diisocyanate comprises toluylene diisocya-nate, ditan-4,4'-vulcabond, to phenylene vulcabond, eylylene diisocyanate, 1,5-naphthalene (naphtylene) vulcabond, 3,3'-dimethyl diphenyl base-4,4'-vulcabond, dimethoxy aniline vulcabond, tetramethyl xylylen vulcabond and similar aromatic diisocyanate; And 1,6-hexamethylene diisocyanate, 2,2,4 and/or (2,4,4)-trimethyl hexamethylene diisocyanate, lysinediisocyanate and similar aliphatic diisocyanate.
Above-mentioned vulcabond can be used by the form of multiple blocking agent isocyanic ester.
The example that per molecule has a polymeric polyisocyanate of three or more isocyanate group comprises isocyanurate trimer, biuret trimer, the trimethylolpropane adduct of above-mentioned vulcabond and analogue; And triphenylmethane triisocyanate, 1-Toluene-2,4-diisocyanate, 4,6-triisocyanate, dimethyl triphenyl methane tetraisocyanate and similar three or multi-functional isocyanic ester.These isocyanate compounds can modified product form use, the product of such as carbodiimide modified, isocyanurate-modified product and biuret modified product, or use with the form of masked isocyanate, namely by the isocyanic ester of multiple blocking agent.
Example as the polyol component of carbamate resins emulsion (a1-1 (c)) initial feed comprises the polycarbonate polyol of the polycarbonate diol as main ingredient, polyvalent alcohol, polycaprolactone polyol, low-molecular-weight polyvalent alcohol, polyether alcohol, polybutadiene polyvalent alcohol and the silicone polyvalent alcohol containing ester bond.
Polycarbonate polyol is the compound obtained according to known method generation polycondensation by known polyvalent alcohol and carbonyl agent.
The example of polyvalent alcohol that can be used as polycarbonate polyol initial feed comprises glycol and trivalent alcohol or more senior polyvalent alcohol.
Can be used as in the polyvalent alcohol of polycarbonate polyol initial feed, the example of glycol comprises 1,3-PD, BDO, 1,5-pentanediol, 1,6-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1,9-nonanediol, decamethylene-glycol and similar straight chain aliphatic diols; 2-methyl isophthalic acid, ammediol, 3-methyl isophthalic acid, 5-pentanediol, neopentyl glycol, 2-ethyl-1,6-hexylene glycol, 2,2-diethyl-1, ammediol, 2-butyl-2-ethyl-1,3-PD, 2-methyl isophthalic acid, 8-ethohexadiol, 2,2,4-trimethylammonium-1,3-pentanediol, 2-ethyl-1,3-hexylene glycol and similar branched aliphatic glycol; 1,3-cyclohexane diol, Isosorbide-5-Nitrae-cyclohexane diol, 1,4 cyclohexane dimethanol and similar alicyclic diol; To xylenediol, to tetrachloro xylenediol (p-tetrachloroxylenediol) and similar aromatic diol; And glycol ether, dipropylene glycol and similar ether glycol.These glycol can be used alone or two or more couplings.
Can be used as in the polyvalent alcohol of polycarbonate polyol initial feed, the example of trivalent alcohol or more higher polyol comprises glycerol, trimethylolethane, TriMethylolPropane(TMP), TriMethylolPropane(TMP) dipolymer and tetramethylolmethane.These trivalent alcohols or more higher polyol can be used alone or two or more couplings.
Known carbonyl agent can be used as the initial feed of polycarbonate polyol.Its specific examples comprises alkylene carbonates, dialkyl carbonate, diaryl carbonate photoreactive gas.These compounds can be used alone, or two or more couplings.Wherein preferred NSC 11801, propylene carbonate, methylcarbonate, diethyl carbonate, dibutyl carbonate, dipheryl carbonate base ester etc.
The polycarbonate diol being used as main initial feed in the present invention by using glycol as unique polyvalent alcohol and carbonyl agent Reactive Synthesis, and can not use trivalent alcohol or more senior polyvalent alcohol.
The diol component of polycarbonate diol can be usually have 6 or more carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and the glycol of also more preferably 6 to 12 carbon atoms.
The example with the glycol of 6 or more carbon atoms comprises the alicyclic diol containing ring alkylidene group with 6 or more carbon atoms, and has the ring alkylidene group containing alkylidene group of 6 or more carbon atoms.
The example with the alicyclic diol containing ring alkylidene group of 6 or more carbon atoms comprises and has 6 or more carbon atoms and the alicyclic diol preferably with 6 to 12 carbon atoms, such as 1,3-cyclohexane diol, Isosorbide-5-Nitrae-cyclohexane diol and 1,4 cyclohexane dimethanol.
Wherein, consider chipping resistance, preferred 1,4 cyclohexane dimethanol.
The example with the aliphatic diol containing alkylidene group of 6 or more carbon atoms comprises and has 6 or more carbon atoms and the aliphatic diol preferably with the straight or branched of 6 to 10 carbon atoms, such as 1,6-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1,9-nonanediol, decamethylene-glycol and similar straight chain aliphatic diols; And 3-methyl isophthalic acid, 5-pentanediol, 2-ethyl-1,6-hexylene glycol, 2,2-diethyl-1, ammediol, 2-butyl-2-ethyl-1,3-PD, 2-methyl isophthalic acid, 8-ethohexadiol, 2,2,4-trimethylammonium-1,3-pentanediol, 2-ethyl-1,3-hexylene glycol and similar branched aliphatic glycol.
Above-mentioned straight chain aliphatic diols or branched aliphatic glycol can use separately or together.
Wherein, consider chipping resistance, preferred straight chain aliphatic diols, particularly preferably 1,6-hexylene glycol.
Relative to diol component total amount, the diol component of polycarbonate diol is preferably containing 90 quality % or more, and the C of particularly preferably 95 quality % or more 6or more higher glycols.
Consider the surface smoothness of gained multilayer film, particularly preferably following polycarbonate diol: react by diol component and carbonyl agent the polycarbonate diol obtained, wherein relative to the total amount of diol component, diol component contains the C of 90 quality % or more 6or more higher glycols, and C 6or more higher glycols contains the alicyclic diol containing ring alkylidene group with 6 or more carbon atoms.
Relative to the total amount of glycol with 6 or more carbon atoms, the consumption with the alicyclic diol containing ring alkylidene group of 6 or more carbon atoms is preferably 50 quality % or more, more preferably 65 quality % to 100 quality %, and particularly preferably 75 quality % to 100 quality %.
Another preferred embodiment in, the example of polycarbonate diol that can be used as carbamate resins emulsion (a1-1 (c)) initial feed comprises the polycarbonate diol with comprising the above-mentioned diol component with the alicyclic diol containing ring alkylidene group of 6 or more carbon atoms and preparing, namely by making containing the C containing ring alkylidene group 6or the diol component of more senior alicyclic diol and carbonyl agent react the polycarbonate diol obtained.
In this embodiment, the example that can be preferably used as the polycarbonate diol of carbamate resins emulsion (a1-1 (c)) initial feed comprises the polycarbonate diol using and prepare containing the alicyclic diol containing ring alkylidene group with 6 or more carbon atoms and the diol component of the aliphatic diol containing alkylidene group with 6 or more carbon atoms, wherein relative to the total amount of diol component, in diol component, the total amount of alicyclic diol and aliphatic diol is 50 quality % or more, namely diol component and carbonyl agent by making the above-mentioned alicyclic diol containing 50 quality % or more and above-mentioned aliphatic diol react the polycarbonate diol obtained.
In this embodiment, further preferred by 1,4 cyclohexane dimethanol as the alicyclic diol containing ring alkylidene group with 6 or more carbon atoms, and by 1,6-hexylene glycol as the aliphatic diol containing alkylidene group with 6 or more carbon atoms.
In this embodiment, the alicyclic diol containing ring alkylidene group with 6 or more carbon atoms is preferably 20:80 to 80:20 with the mass ratio of the aliphatic diol containing alkylidene group with 6 or more carbon atoms.
Another preferred embodiment in, example as the polycarbonate diol of carbamate resins emulsion (a1-1 (c)) initial feed comprises the polycarbonate diol component using and prepare containing the aliphatic diol containing alkylidene group with 6 or more carbon atoms and the diol component of the alicyclic diol containing ring alkylidene group with 6 or more carbon atoms, wherein relative to the total amount of diol component, in diol component, the total amount of aliphatic diol and alicyclic diol is 50 quality % or more.
In this embodiment, preferably by 1,6-hexylene glycol as the aliphatic diol containing alkylidene group with 6 or more carbon atoms, and by 1,4 cyclohexane dimethanol as the alicyclic diol containing ring alkylidene group with 6 or more carbon atoms.
In this embodiment, the aliphatic diol containing alkylidene group with 6 or more carbon atoms is preferably 20:80 to 80:20 with the mass ratio of the alicyclic diol containing ring alkylidene group with 6 or more carbon atoms.
In polyol component, the example containing the polyvalent alcohol of ester bond comprises polyester polyol and polyester polycarbonate polyols.
The example of polyester polyol comprises those that to become ester cpds such as its ester, acid anhydrides or halogenide to be obtained by direct esterification and/or transesterification reaction with polycarboxylic acid or its by polyvalent alcohol.
The example that can be used as the polyvalent alcohol of polyester polyol initial feed comprises ethylene glycol, 1, 2-propylene glycol, 1, ammediol, 2-methyl isophthalic acid, ammediol, 2-butyl-2-ethyl-1, ammediol, 1, 4-butyleneglycol, neopentyl glycol, 3-methyl-2, 4-pentanediol, 2, 4-pentanediol, 1, 5-pentanediol, 3-methyl isophthalic acid, 5-pentanediol, 2-methyl-2, 4-pentanediol, 2, 4-diethyl-1, 5-pentanediol, 1, 6-hexylene glycol, 1, 7-heptanediol, 3, 5-heptanediol, 1, 8-ethohexadiol, 2-methyl isophthalic acid, 8-ethohexadiol, 1, 9-nonanediol, 1, 10-decanediol, glycol ether, triglycol and similar aliphatic diol compound, cyclohexanedimethanol, cyclohexane diol and similar alicyclic diol compound, trimethylolethane, trimethyl propane, hexitol compound, pentitol compound, glycerol, tetramethylolmethane, the first alkylol cpd of tetra methylol propane and similar ternary or more.
The example of the polycarboxylic acid or its one-tenth ester cpds that can be used as polyester polyol initial feed comprises oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, dodecanedioic acid, 2-methyl-succinic acid, 2-methyl-hexanodioic acid, 3-methyl-hexanodioic acid, 3-methylglutaric acid, 2-methyl suberic acid, 3,8-dimethyl sebacic acid, 3,7-dimethyl sebacic acid, hydrogenated dimer acids, dimeracid and similar aliphatic dicarboxylic acid compound; Phthalic acid, terephthalic acid, m-phthalic acid, naphthalene-dicarboxylic acid and similar aromatic dicarboxylic acid compound; 1,2-cyclopentane dicarboxylic acid, 1,3-cyclopentane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, Isosorbide-5-Nitrae-dicarboxy-methyl hexanaphthene, Na Dike acid (nadic acid), methyl Na Dike acid and similar alicyclic dicarboxylic acid's compound; Tricarboxylic acid compound (such as the tripolymer of trimellitic acid, trimesic acid and Castor Oil Fatty Acid) and similar polycarboxylic acid; The acid anhydrides of these polycarboxylic acids; The halogenide of polycarboxylic acid, such as muriate and bromide; The lower member ester of polycarboxylic acid, such as methyl esters, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester and pentyl ester; γ-hexalactone, δ-caprolactone, 6-caprolactone, dimethyl-E-caprolactone, δ-valerolactone, γ-valerolactone, gamma-butyrolactone and similar lactone compound.
In polyol component, the example of polycaprolactone polyol comprises the ring-opening polymerization polymer of caprolactone, such as polycaprolactone glycol.
In polyol component, the example of low molecular weight polyols comprises the polyvalent alcohol of such as polyester polyol.
In polyol component, the example of polyester polyol comprises oxyethane and/or the propylene oxide adduct of above-mentioned low molecular weight polyols and polytetramethylene glycol.
In polyol component, the example of polybutadiene polyol be well-known in the art those.
The example of silicone polyol comprises in molecule the end hydroxyl silicone oil compound with siloxane bond.
Carboxylic glycol can be used as polyol component.Carboxylic glycol is used for hydrophilic group to introduce polyurethane molecular.This hydrophilic group is carboxyl.Its specific examples comprises dimethylol propionic acid, dimethylolpropionic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid.
In the present invention, consider the surface smoothness of coatingsurface, based on the total amount of polyol component, in carbamate resins emulsion (a1-1 (c)), the amount of polycarbonate diol component is preferably 50 quality % or more, particularly preferably 75 quality % to 100 quality %, and also more preferably 90 quality % to 100 quality %.
If needed, except polyisocyanate component and polyol component, amine component can be used to prepare carbamate resins emulsion (a1-1 (c)).The example of amine component comprises mono-amine compound and diamine compound.
Mono-amine compound is not particularly limited, and known mono-amine compound can be used alone or by two kinds or more kinds ofly to combinationally use.The example of mono-amine compound comprises ethamine, propylamine, 2-propylamine, butylamine, 2-butylamine, TERTIARY BUTYL AMINE, isobutylamine and similar alkanamine; Aniline, monomethylaniline, nonox, naphthylamines and similar aromatic amine; Hexahydroaniline, methyl cyclohexylamine and similar aliphatic cyclic amine; 2-methoxyethyl amine, 3 methoxypropyl amine, 2-(2-methoxy ethoxy) ethamine and similar ether amine; Thanomin, Propanolamine, butylethanolamine, 1-amino-2-methyl-2-propyl alcohol, 2-amino-2-methyl propyl alcohol, diethanolamine, diisopropanolamine (DIPA), dimethylaminopropyl thanomin, dipropanolamine, N-Mono Methyl Ethanol Amine, N-ehtylethanolamine and similar alkanolamine etc.Wherein, alkanolamine is owing to making polyurethane molecular have good dispersion stability but preferred.Consider the stability of supply, preferred 2-monoethanolamine and diethanolamine.
Diamine compound is not particularly limited, and known diamine compound can be used alone or two or more are combinationally used.The example of diamine compound comprises the lower molecular weight diamine compound by obtaining with the alcoholic extract hydroxyl group in amino replacement above illustrative low molecular weight diols, such as quadrol and propylene diamine; Polypropyleneoxide diamine, polyethyleneoxide diamine and similar polyether diamine compound; Menthane diamines, isophorone diamine, norbornylene diamines, two (4-amino-3-methyldicyclohexyl) methane, diamino-dicyclohexyl methane, two (amino methyl) hexanaphthene, 3, two (the 3-aminopropyl) 2 of 9-, 4,8,10-tetra-oxaspiro (5,5) undecane and similar alicyclic diamine compound; M-xylene diamine, α-(position/contraposition aminophenyl) ethamine, a position phenylenediamine, diaminodiphenyl-methane, diaminodiphenylsulfone(DDS), diamino diethyl-dimethyl ditan, diamino diethyl ditan, dimethylthiotoluenediamine, diethyl toluene diamine, α, α '-bis-(4-aminophenyl)-to diisopropyl benzene and similar aromatic diamine compound; Hydrazides class; And the dicarboxylic acid dihydrazide compound of dicarboxylic acid such as being formed between the polycarboxylic acid of polyester polyol and hydrazides class.In diamine compounds, consider operability, preferred lower molecular weight diamine compounds.Particularly preferably quadrol.
And, can use in carboxyl as required and component.In carboxyl with component be and the carboxyl reaction in carboxylic glycol, and form the basic cpd of hydrophilic salts.The example comprises Trimethylamine 99, triethylamine, Tributylamine and similar trialkylamine compound, N, N-dimethylethanolamine, N, N-dimethyl propanol amine, N, N-dipropylethanolamine, 1-dimethylamino-2-methyl-2-propanol and similar N, N-dialkyl amine compound, N-alkyl-N, N-dialkanol amine compound, three triacontanol amine compounds (such as trolamine) and similar tertiary amine compound, ammonia, trimethylammonium hydroxide, sodium hydroxide, potassium hydroxide and lithium hydroxide.Wherein, because the dispersion stabilization of gained carbamate resins emulsion (a1-1 (c)) is good, therefore preferred tertiary amine compound.
In addition to the aforementioned components, carbamate resins emulsion (a1-1 (c)) can also further containing making polyurethane molecular form the interior branch agent of branched structure and/or make polyurethane molecular form the internal crosslinking agent of crosslinking structure.Can preferably by ternary or more higher polyol be used as such interior branch agent and internal crosslinking agent.The example comprises TriMethylolPropane(TMP).
The preparation method of carbamate resins emulsion (a1-1 (c)) is not particularly limited, and can be selected from known method.Preferred preparation method is included in reacting in inertia and having synthetic prepolymer or polymkeric substance in the solvent of high-hydrophilic, then prepolymer or polymkeric substance is added to the water to be scattered in water.The specific examples of such method comprises method (A), is included in by polyisocyanate component and polyol component synthetic prepolymer in above-mentioned solvent, and prepolymer is reacted with the amine component used as required in water; With method (B), comprise by polyisocyanate component, polyol component and the amine component synthetic polymer that uses as required, then polymkeric substance is added to the water to be dispersed in water.Can be added to the water in advance before Xiang Shuizhong adds prepolymer or polymkeric substance with component in using as required, also can be added to the water after Xiang Shuizhong adds prepolymer or polymkeric substance.
Use in preferred preparation method, to reaction in inertia and the example with the solvent of high-hydrophilic comprises acetone, methylethylketone, diox, tetrahydrofuran (THF) and METHYLPYRROLIDONE.Usually, relative to the total amount of the starting raw material for the preparation of prepolymer, the consumption of such solvent is 3 quality % to 100 quality %.
In above-mentioned preparation method, its proportion of composing is not particularly limited.The mol ratio of isocyanate group in isocyanate-reactive group and polyisocyanate component in polyol component and amine component when proportion of composing can be expressed as reaction.The mol ratio of isocyanate-reactive group and isocyanate group is preferably 0.5:1 to 2.0:1.If this is the quantity not sufficient of unreacted isocyanate group in polyurethane molecular due to dispersion, then when using as coating composition, the clinging power of film and/or intensity may reduce; And if the excessive existence of unreacted isocyanate group, then isocyanate group bring impact may to the dispersion stabilization of coating composition and/or performance.In polyol component, in isocyanate-reactive group and polyisocyanate component, the mol ratio of isocyanate group is preferably 0.3:1 to 1.0:1, and more preferably 0.5:1 to 0.9:1.In addition, in the amine component used as required, in isocyanate-reactive group and polyisocyanate component, the mol ratio of isocyanate group is preferably 0.1:1 to 1.0:1, and more preferably 0.2:1 to 0.5:1.
In addition, by the carboxyl that uses as required and the neutralization ratio of component, be set in and gained carbamate resins emulsion (a1-1 (c)) is had in the scope of sufficient dispersion stabilization.Carboxyl in carboxylic glycol relative to every mole, is preferably 0.5 equivalent to 2.0 equivalent with the amount of component in carboxyl, is more preferably 0.7 equivalent to 1.5 equivalent.
In order to make the dispersiveness of carbamate resins emulsion (a1-1 (c)) stablize, one or more emulsifying agents can be used, such as tensio-active agent.Although particle diameter is not particularly limited, in order to keep good dispersion state, particle diameter is preferably less than 1 μm, more preferably below 500nm.
The example of spendable emulsifying agent comprises the known tensio-active agent for carbamate resins emulsion, such as anion surfactant, nonionogenic tenside, cats product, amphoterics, polymeric surface active agent and reactive surfactant.In these tensio-active agents, for reducing costs and obtaining good emulsifying, preferred anionic tensio-active agent, nonionogenic tenside and cats product.
The example of anion surfactant comprises sodium lauryl sulphate, dodecyl sulphate potassium, ammonium lauryl sulfate and similar alkylsurfuric acid salt compound; Brij-35 sodium sulfate; Sulforicinoleic acid sodium; An alkali metal salt of sulfonated olefins, the ammonium salt of sulfonated olefins and similar alkylsulfonate; Sodium laurate, triethanolamine oleate, trolamine sylvate and similar soap; The alkali metal sulfates of benzene sulfonic acid sodium salt, alkaline phenol hydroxy vinyl and similar alkylaryl sulphonate; Senior alkyl naphthalenesulfonate; Naphthalene sulfonic acid formaldehyde condensation polymer; Dialkyl sulfosuccinates; Laureth sulfate and polyxyethylated aryl-sulfate.
The example of nonionogenic tenside comprises C 1-C 18alcohol-oxyethane and/or propylene oxide adduct, alkyl phenol-ethylene oxide and/or propylene oxide adduct, aklylene glycol and/or Alkylenediamine-oxyethane and/or propylene oxide adduct.
Form the C of nonionogenic tenside 1-C 18the example of alcohol comprises methyl alcohol, ethanol, propyl alcohol, 2-propyl alcohol, butanols, 2-butanols, the trimethyl carbinol, amylalcohol, primary isoamyl alcohol, tertiary amyl alcohol, hexanol, octanol, decyl alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol and stearyl alcohol; The example of alkylphenol comprises phenol, methylphenol, 2,4-DI-tert-butylphenol compounds, 2,5-DI-tert-butylphenol compounds, 3,5-DI-tert-butylphenol compounds, 4-(1,3-tetramethyl butyl) phenol, 4-isooctyl phenol, 4-nonylphenol, 4-tert-octyl phenol, 4-dodecyl phenol, 2-(3,5-dimethyl heptyl) phenol, 4-(3,5-dimethyl heptyl) phenol, naphthols, dihydroxyphenyl propane and Bisphenol F.The example of aklylene glycol comprises ethylene glycol, 1,2-propylene glycol, 1, ammediol, 2-methyl isophthalic acid, ammediol, 2-butyl-2-ethyl-1,3-PD, 1,4-butyleneglycol, neopentyl glycol, 1,5-pentanediol, 3-methyl isophthalic acid, 5-pentanediol, 2,4-diethyl-1,5-pentanediol and 1,6-hexylene glycol; The example of Alkylenediamine comprises the aklylene glycol that wherein alcohol hydroxyl group is replaced by amino.In addition, oxyethane and propylene oxide adduct can be random adductss also can be block adducts.
The example of cats product comprises primary amine to tertiary ammonium salt, pyridinium salt, Fixanol, haloalkane quaternary ammonium salt and similar quaternary ammonium salt.
Although the usage quantity of these emulsifying agents is not particularly limited, can measure use arbitrarily, the mass ratio of emulsifying agent and carbamate resins is preferably 0.01:1 to 0.3:1, and more preferably 0.05:1 to 0.2:1.This is due to when emulsifying agent/carbamate resins ratio is less than 0.05, dispersed possibility not, and when emulsifying agent/carbamate resins ratio is more than 0.3, the performance such as water tolerance, intensity, elongation at break of the film obtained by water-based paint compositions may reduce.
In addition, the solids content of carbamate resins emulsion (a1-1 (c)) is not particularly limited, and can select arbitrary value.For making dispersiveness and coating well, solids content is preferably 10 quality % to 50 quality %, is more preferably 20 quality % to 40 quality %.
Consider the smoothness of gained film, the weight-average molecular weight being scattered in the carbamate resins in carbamate resins emulsion (a1-1 (c)) is preferably 2,000 to 50,000, and is more preferably 3,000 to 40,000.In addition, hydroxyl value is also not particularly limited, and can select arbitrary value.Hydroxyl value represents with the KOH consumption (mg) of every gram of resin, and is generally 0 to 100mgKOH/g.
In this manual, number-average molecular weight and weight-average molecular weight are by gel permeation chromatography, use the conversion value that tetrahydrofuran (THF) also uses the polystyrene with known molecular amount to obtain as object of reference as solvent.
Consider smoothness and the reflection sharpness of gained multilayer film, relative to the solids content of binder ingredients (a1), in binder ingredients (a1), the amount of carbamate resins emulsion (a1-1 (c)) is preferably 10 quality % or more, more preferably 15 quality % to 60 quality %, and even more preferably 15 quality % to 55 quality %.
Acrylic resin, vibrin, Synolac and the urethane resin except carbamate resins emulsion (a1-1 (c)) can be comprised as the example of other film-forming resin of binder ingredients (a1) together with carbamate resins emulsion (a1-1 (c)), it preferably has crosslinkable functionality, such as hydroxyl, carboxyl and epoxy group(ing).When film-forming resin has hydroxyl, its hydroxyl value is preferably about 1mg KOH/g to 200mg KOH/g, more preferably from about 2mg KOH/g to 180mgKOH/g, and even more preferably from about 5mg KOH/g to 170mg KOH/g.In addition, when film-forming resin has the acidic-group of such as carboxyl, its acid number is preferably about 5mg KOH/g to 150mg KOH/g, more preferably from about 10mg KOH/g to 100mg KOH/g, and even more preferably from about 15mg KOH/g to 80mg KOH/g.
Except film-forming resin, linking agent can also be used as binder ingredients (a1).When linking agent is used as binder ingredients (a1) a part of, film-forming resin usually can be have such as hydroxyl, carboxyl or epoxy group(ing) crosslinkable functionality and can react with linking agent thus form the resin (matrix resin) being cross-linked film.
Binder ingredients (a1) is particularly preferably containing the acrylic resin (a1-2 (c)) of hydroxyl and/or the vibrin (a1-3 (c)) of hydroxyl.Consider the smoothness and reflection sharpness of improving film, more preferably by the acrylic resin (a1-2 (c)) of hydroxyl and vibrin (a1-3 (the c)) coupling of hydroxyl.During coupling, relative to the total amount of the acrylic resin (a1-2 (c)) of hydroxyl with the vibrin (a1-3 (c)) of hydroxyl, the ratio of the acrylic resin (a1-2 (c)) of hydroxyl and the vibrin (a1-3 (c)) of hydroxyl is preferably about 10:90 to 90:10 by quality %, and is particularly preferably 20:80 to 80:20 by quality %.
The type, consumption etc. of the acrylic resin (a1-1 (a)) of the hydroxyl described in the first embodiment can be used in the acrylic resin (a1-2 (c)) of hydroxyl.
The type, preparation method, consumption etc. of the acrylic resin (a1-1 (a)) of the hydroxyl described in the first embodiment can be used in the vibrin (a1-3 (c)) of hydroxyl.
The type, consumption etc. of the linking agent described in the first embodiment also can be used in this embodiment.
pigment (a2)
The type, consumption etc. of the pigment (a2) described in the first embodiment also can be used in this embodiment.
If needed, water-based colored coating composition (A) can containing the additive for coating composition, such as thickening material, curing catalysts, UV absorption agent, photostabilizer, defoamer, softening agent, surface conditioner and antisettling agent.As for the type, consumption etc. of these additives of coating composition, can use described in the first embodiment those.The preparation method of water-based colored coating composition (A) described in the first embodiment and the condition of coating process also can be used in this embodiment, except binder ingredients (a1) is containing carbamate resins emulsion (a1-1 (c)) and the optionally acrylic resin (a1-2 (c)) of hydroxyl and/or the vibrin (a1-3 (c)) of hydroxyl.
operation (2) is to (4)
As for the coating composition, coating process, heating means etc. that use in operation (2) to (4), condition described in the first embodiment also can be used in this embodiment.
In the method for formation multilayer film of the present invention, even if when the pre-heating technique after application water-based colored coating composition (A) is omitted, and when being coated on the painted film containing a large amount of solvent by the water-based paint compositions (B) containing effect pigment, still can form the multilayer film with excellent smoothness, reflection sharpness and water-repellancy.The chances are for this because the use of the water-based colored coating composition (A) containing above-mentioned specific carbamate resins emulsion suppresses the painted film of gained to expand due to water and organic solvent.In addition, application causes forming film on painted film containing water-based paint compositions (B) to the film thickness containing effect pigment of a large amount of effect pigment, wherein resin Composition and effect pigment exist with high-density, make the solvent in painted film be difficult to entrance effect film.In addition, the shipwreck in painted film with entrance effect film because containing the water-based paint compositions (B) of effect pigment containing relatively large hydrophobic solvent (b3).Due to these reasons, prevent water-based colored coating composition (A) and form mixolimnion containing the water-based paint compositions (B) of effect pigment.
(IV) wherein the vinylformic acid of water-based colored coating composition (A) containing specific hydroxyl is set fat liquor and specific dead front type contain the enforcement side of the carbamate resins emulsion of isocyanate group formula
Another preferred embodiment in, the invention provides the method for the formation multilayer film according to following item 1D to 5D:
Item 1D. forms the method for multilayer film, comprises following operation (1) to (4):
(1) application water-based colored coating composition (A) on coated article, forms uncured painted film;
This water-based colored coating composition (A) containing binder ingredients (a1) and pigment (a2),
Binder ingredients (a1) comprise Emulsion acrylic resin (a1-1 (d)) that acid number is 25mg KOH/g or less hydroxyl and dead front type containing isocyanic ester carbamate resins emulsion (a1-2 (d)) as it at least partially, wherein, described dead front type uses the polyol component of the polyisocyanate component containing alicyclic diisocyanate and the polycarbonate diol containing 50 quality % or more to be prepared from as starting raw material containing the carbamate resins emulsion (a1-2 (d)) of isocyanic ester;
(2) the painted film that not preheating is uncured, on the uncured painted film formed in operation (1), application comprises the water-based paint compositions (B) containing effect pigment of binder ingredients (b1), effect pigment (b2) and hydrophobic solvent (b3), after forming solidification, film thickness is the uncured effect film of 7 μm to 13 μm, wherein, relative to the solids content of the binder ingredients (b1) of 100 mass parts, effect pigment (b2) is 15 mass parts to 30 mass parts, and hydrophobic solvent (b3) is 25 mass parts to 60 mass parts;
(3) transparent paint coating composition (C) on the uncured effect film formed in operation (2), forms uncured transparent coating; And
(4) uncured painted film, uncured effect film and the uncured transparent coating that are formed respectively in heating process (1) to (3), three-layer coated to solidify this simultaneously.
The method of the formation multilayer film of item 2D. according to item 1D, wherein the Emulsion acrylic resin (a1-1 (d)) of hydroxyl is Structure of Core/shell Emulsion, it has core part and shell part, described core part is multipolymer (I), the per molecule of polymerizable unsaturated monomer and 70 quality % to 99.9 quality % that the per molecule comprising 0.1 quality % to 30 quality % has two or more polymerizable unsaturated groups has the polymerizable unsaturated monomer of a polymerizable unsaturated group as copolymer component, and described shell part is multipolymer (II), comprise the polymerizable unsaturated monomer of the hydroxyl of 1 quality % to 40 quality %, the carboxylic polymerizable unsaturated monomer of 1 quality % to 30 quality % and other polymerizable unsaturated monomer of 30 quality % to 98 quality % are as copolymer component.
The method of the formation multilayer film of item 3D. according to item 1D or 2D, wherein dead front type is 2,000 to 50,000 containing the weight-average molecular weight of the carbamate resins emulsion (a1-2 (d)) of isocyanic ester.
The method of the formation multilayer film of item 4D. according to any one of item 1D to 3D, wherein polycarbonate diol obtains by making diol component and the reaction of carbonyl agent, relative to diol component total amount, described diol component comprises the glycol with 6 or more carbon atoms of 90 quality % or more, and the glycol with 6 or more carbon atoms comprises the alicyclic diol containing ring alkylidene group with 6 or more carbon atoms.
The method of the formation multilayer film of item 5D. according to any one of item 1D to 4D, wherein pigment (a2) comprises titanium dioxide and/or barium sulfate, and the solids content of binder ingredients (a1) relative to 100 mass parts, the total content of titanium dioxide and barium sulfate is 50 mass parts to 150 mass parts.
The coated article addressed in " coated article " item of above-mentioned first embodiment also can be used in this embodiment.
water-based colored coating composition (A)
The water-based colored coating composition (A) of coated article to be coated on can be the coating composition such as comprising binder ingredients (a1), pigment (a2) and the optional additive for coating composition etc.
binder ingredients (a1)
In the present embodiment, it is the Emulsion acrylic resin (a1-1 (d)) of 25mg KOH/g or less hydroxyl that binder ingredients (a1) comprises as its acid number at least partially, and the dead front type using polyisocyanate component and polyol component to prepare as initial feed is containing the carbamate resins emulsion (a1-2 (d)) of isocyanic ester.Particularly, in the present embodiment, polyisocyanate component contains alicyclic diisocyanate, and polyol component contains the polycarbonate diol relative to polyol component total amount 50 quality %.
If needed, the known film-forming resin being used as coating composition binder ingredients can also be used as binder ingredients (a1).Non-crosslinked type resin and crosslinked resin all can use.
the Emulsion acrylic resin (a1-1 (d)) of hydroxyl
Can by using known method, such as, emulsion polymerization in water, the polymerizable unsaturated monomer of copolymerization hydroxyl with can prepare the Emulsion acrylic resin (a1-1 (d)) of hydroxyl with the another kind of polymerizable unsaturated monomer of the polymerizable unsaturated monomer copolymerization of hydroxyl.
Those of the acrylic resin (a1-1 (a)) relating to hydroxyl that describes in the first embodiment can be used as hydroxyl polymerizable unsaturated monomers and can with other polymerizable unsaturated monomer of the polymerizable unsaturated monomer copolymerization of hydroxyl.
Relative to the total amount of monomer component, the amount of the polymerizable unsaturated monomer of the hydroxyl used in the Emulsion acrylic resin (a1-1 (d)) preparing hydroxyl is preferably about 0.1 quality % to 50 quality %, more preferably from about 0.5 quality % to 40 quality %, and even more preferably from about 1 quality % to 30 quality %.
Consider the water-repellancy of the stability in storage of coating composition, gained film and prevent water-based colored coating composition (A) and form mixolimnion containing the water-based paint compositions (B) of effect pigment, the acid number of the Emulsion acrylic resin (a1-1 (d)) of hydroxyl is preferably 25mg KOH/g or less, more preferably from about 0.1mg KOH/g to 20mg KOH/g, and even more preferably from about 1mgKOH/g to 15mg KOH/g.
And, consider the chipping resistance and water-repellancy etc. of gained film, the hydroxyl value of the Emulsion acrylic resin (a1-1 (d)) of hydroxyl is preferably about 1mg KOH/g to 200mg KOH/g, more preferably from about 3mg KOH/g to 100mg KOH/g, and even more preferably from about 5mg KOH/g to 50mg KOH/g.
Relative to the solids content of binder ingredients (a1), in water-based colored coating composition (A), the amount of the Emulsion acrylic resin (a1-1 (d)) of hydroxyl is preferably about 2 quality % to 70 quality %, more preferably from about 10 quality % to 65 quality %, and even more preferably from about 20 quality % to 60 quality %.
Consider smoothness and water-repellancy, Emulsion acrylic resin (a1-1 (d)) the preferably core/shell type emulsion of hydroxyl.
The Sutable examples of the Emulsion acrylic resin of core/shell type hydroxyl is the Emulsion acrylic resin (a1-1'(d) of core/shell type hydroxyl), its core part comprises per molecule to have the multipolymer (I) of polymerizable unsaturated monomer as copolymer component that the polymerizable unsaturated monomer of two or more polymerizable unsaturated group and per molecule have a polymerizable unsaturated group, shell part is the polymerizable unsaturated monomer comprising hydroxyl, carboxylic polymerizable unsaturated monomer and the multipolymer (II) of other polymerizable unsaturated monomer as copolymer component.
Per molecule has two or more polymerizable unsaturated group, and the example that can be used as the polymerizable unsaturated monomer of core multipolymer (I) monomer comprises allyl group (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, triglycol two (methyl) acrylate, Tetraglycol 99 two (methyl) acrylate, 1,3 butylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, BDO two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, glycerol two (methyl) acrylate, 1,1,1-trimethylolethane two (methyl) acrylate, 1,1,1-trimethylolethane trimethacrylate (methyl) acrylate, 1,1,1-trimethylolpropane tris (methyl) acrylate, cyanacrylate, diallyl terephthalic acid's salt, divinylbenzene etc.These monomers can be used alone or two or more couplings.
The effect that per molecule has the polymerizable unsaturated monomer of two or more polymerizable unsaturated group is for core multipolymer (I) provides crosslinking structure.Although the amount that per molecule has the polymerizable unsaturated monomer of two or more polymerizable unsaturated group suitably can be determined according to the degree of crosslinking of the core multipolymer (I) expected, but the total mass of the monomer relative to composition core multipolymer (I), the amount of polymerizable unsaturated monomer is preferably about 0.1 quality % to 30 quality % usually, more preferably from about 0.5 quality % to 10 quality %, and even more preferably from about 1 quality % to 7 quality %.
In order to suppress the metalmark of gained film, the polymerizable unsaturated monomer that per molecule has two or more polymerizable unsaturated group is preferably the monomer of amide-containing, such as methylene radical two (methyl) acrylamide and ethylene (methyl) acrylamide.During use, relative to the total mass of monomer of composition core multipolymer (I), the amount of the monomer of amide-containing is preferably about 0.1 quality % to 25 quality %, more preferably from about 0.5 quality % to 8 quality %, and even more preferably from about 1 quality % to 4 quality %.
The polymerizable unsaturated monomer that per molecule as the monomer of core multipolymer (I) has a polymerizable unsaturated group is the polymerizable unsaturated monomer can with the polymerizable unsaturated monomer copolymerization of two or more polymerizable unsaturated group.
The specific examples that per molecule has the polymerizable unsaturated monomer of a polymerizable unsaturated group comprises monomer (i) to (xi) and (xiii) to (xvii), they are as can with the polymerizable unsaturated monomer cited by other polymerizable unsaturated monomer of the polymerizable unsaturated monomer copolymerization of hydroxyl in the explanation of the Emulsion acrylic resin (a1-1 (a)) of hydroxyl, the polymerizable unsaturated monomer except the polymerizable unsaturated monomer that per molecule has two or more polymerizable unsaturated group.These monomers can according to the Emulsion acrylic resin of core/shell type hydroxyl (a1-1'(d)) performance need to be used alone or by two or more couplings.
Shell multipolymer (II) comprises the polymerizable unsaturated monomer of hydroxyl, the polymerizable unsaturated monomer containing acid (such as carboxyl), and other polymerizable unsaturated monomer, as copolymer component.
Hydroxyl that can be crosslinked with solidifying agent (B) as the polymerizable unsaturated monomer of the hydroxyl of shell multipolymer (II) monomer is introduced in water-dispersible acrylic's resin, thus plays the effect of the stability improving coating waterproofing and improve water-dispersible acrylic's resin in water medium.The example of the polymerizable unsaturated monomer of hydroxyl comprises the mono-esterification product of (methyl) vinylformic acid and the glycol containing 2 to 8 carbon atoms, such as 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 3-hydroxypropyl (methyl) acrylate and 4-hydroxyl butyl (methyl) acrylate; The 6-caprolactone modified product of (methyl) vinylformic acid and the mono-esterification product containing the glycol of 2 to 8 carbon atoms; N-methylol (methyl) acrylamide; Vinyl carbinol; There is (methyl) acrylate etc. that end is the polyoxyethylene chain of hydroxyl.These monomers can be used alone or two or more couplings.The preferred embodiment of the polymerizable unsaturated monomer of hydroxyl comprises 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 3-hydroxypropyl (methyl) acrylate, 4-hydroxyl butyl (methyl) acrylate etc.
In order to make the Emulsion acrylic resin of core/shell type hydroxyl (a1-1'(d)) there is excellent stability in water medium and make film have excellent water-repellancy, relative to the total mass of the monomer of composition shell multipolymer (II), the amount of the polymerizable unsaturated monomer of hydroxyl is preferably about 1 quality % to 40 quality %, more preferably from about 4 quality % to 25 quality %, and even more preferably from about 7 quality % to 19 quality %.
Specific examples as the carboxylic polymerizable unsaturated monomer of shell multipolymer (II) monomer is identical with the example of the above-mentioned monomer for core multipolymer (I).More specifically, as with the polymerizable unsaturated monomer of other polymerizable unsaturated monomer example of the polymerizable unsaturated monomer copolymerization of hydroxyl, can using carboxylic, polymerizable unsaturated monomer (x) in the explanation of the Emulsion acrylic resin (a1-1 (a)) of hydroxyl.Particularly preferably vinylformic acid and/or methacrylic acid are as carboxylic polymerizable unsaturated monomer.By using carboxylic polymerizable unsaturated monomer in shell, the Emulsion acrylic resin (a1-1'(d) of gained core/shell type hydroxyl) in water medium, become stable.
In order to make the Emulsion acrylic resin of core/shell type hydroxyl (a1-1'(d)) there is excellent stability in water medium, and make film have excellent water-repellancy, relative to the total mass of the monomer of composition shell multipolymer (II), during use, the amount of carboxylic polymerizable unsaturated monomer is preferably about 1 quality % to 30 quality %, more preferably from about 5 quality % to 25 quality %, and even more preferably from about 7 quality % to 19 quality %.
As the polymerizable unsaturated monomer that other polymerizable unsaturated monomer of the monomer of shell multipolymer (II) is except the polymerizable unsaturated monomer of hydroxyl and carboxylic polymerizable unsaturated monomer.The example of these monomers comprises alkyl or cycloalkyl (methyl) acrylate, such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate and (methyl) tert-butyl acrylate, alkyl or cycloalkyl (methyl) acrylate, the such as just own ester of (methyl) vinylformic acid, (methyl) Octyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) tridecyl acrylate, (methyl) dodecylacrylate, (methyl) octadecyl acrylate, (methyl) vinylformic acid isooctadecane base ester, (methyl) cyclohexyl acrylate, (methyl) acrylic methyl cyclohexyl, (methyl) t-butylcyclohexyl ester, (methyl) vinylformic acid cyclo-dodecyl ester and (methyl) vinylformic acid three ring ester in the last of the ten Heavenly stems, containing the polymerizable unsaturated compound of isobornyl, such as (methyl) isobornyl acrylate, containing the polymerizable unsaturated compound of adamantyl, such as (methyl) vinylformic acid adamantane esters, and contain the polymerizable unsaturated monomer of aromatic nucleus, such as (methyl) benzyl acrylate, vinylbenzene, alpha-methyl styrene and Vinyl toluene.These monomers can be used alone or two or more couplings.Particularly preferably at least one of other polymerizable unsaturated monomer is hydrophobic polymerizable unsaturated monomer.
In this manual, hydrophobic polymerizable unsaturated monomer be have containing 6 or more carbon atom, preferably 6 to 18 carbon atoms straight chain, side chain or ring-type is saturated or the polymerizable unsaturated monomer of unsaturated alkyl, except having the monomer of hydrophilic group, the polymerizable unsaturated monomer of such as hydroxyl.The example of these monomers comprises alkyl or cycloalkyl (methyl) acrylate, the such as just own ester of (methyl) vinylformic acid, (methyl) Octyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) tridecyl acrylate, (methyl) dodecylacrylate, (methyl) octadecyl acrylate, (methyl) vinylformic acid isooctadecane base ester, (methyl) cyclohexyl acrylate, (methyl) acrylic methyl cyclohexyl, (methyl) t-butylcyclohexyl ester, (methyl) vinylformic acid cyclo-dodecyl ester and (methyl) vinylformic acid three ring ester in the last of the ten Heavenly stems, containing the polymerizable unsaturated compound of isobornyl, such as (methyl) isobornyl acrylate, containing the polymerizable unsaturated compound of adamantyl, such as (methyl) vinylformic acid adamantane esters, and contain the polymerizable unsaturated monomer of aromatic nucleus, such as (methyl) benzyl acrylate, vinylbenzene, alpha-methyl styrene and Vinyl toluene.These monomers can be used alone or two or more couplings.
In order to improve the reflection sharpness of gained film, hydrophobic polymerizable unsaturated monomer preferably have containing the alkyl of 6 to 18 carbon atoms polymerizable unsaturated monomer and/or there is the polymerizable unsaturated monomer of aromatic nucleus.Particularly preferably vinylbenzene.
In order to make the Emulsion acrylic resin of core/shell type hydroxyl (a1-1'(d)) there is excellent stability in water medium, and make film have excellent water-repellancy, when being used as the monomer of shell multipolymer (II), relative to the total mass of the monomer of composition shell multipolymer (II), the amount of hydrophobic polymerizable unsaturated monomer is preferably about 5 quality % to 50 quality %, more preferably from about 7 quality % to 40 quality %, and even more preferably from about 9 quality % to 30 quality %.
In order to improve the effect (gloss) of gained film, preferably do not use per molecule to have polymerizable unsaturated monomer other polymerizable unsaturated monomer as composition shell multipolymer (II) of two or more polymerizable unsaturated group, thus form noncrosslinking multipolymer (II).
In order to improve reflection sharpness and the effect (gloss) of gained film, based on solid, the Emulsion acrylic resin (a1-1'(d) of core/shell type hydroxyl) in the ratio of multipolymer (I) and multipolymer (II) be preferably about 5/95 to 95/5, more preferably from about 10/90 to 90/10, also more preferably from about 50/50 to 85/15, and particularly preferably about 65/35 to 80/20.
Consider the water-repellancy of the stability in storage of coating composition, gained film and prevent the painted film of water-based colored coating composition (A) from forming mixolimnion with the effect film of the water-based paint compositions (B) containing effect pigment, the Emulsion acrylic resin (a1-1'(d) of core/shell type hydroxyl) acid number be preferably about 25mg KOH/g or less, more preferably from about 0.1mg KOH/g to 20mgKOH/g, and even more preferably from about 1mg KOH/g to 15mg KOH/g.
Consider the chipping resistance of the excellence of gained film, water-repellancy etc., the Emulsion acrylic resin (a1-1'(d) of core/shell type hydroxyl) hydroxyl value be preferably about 1mg KOH/g to 200mgKOH/g, more preferably from about 3mg KOH/g to 100mg KOH/g, and even more preferably from about 5mgKOH/g to 50mg KOH/g.
Relative to the solids content of binder ingredients (a1), the Emulsion acrylic resin (a1-1'(d) of core/shell type hydroxyl in water-based colored coating composition (A)) amount be preferably about 2 quality % to 70 quality %, more preferably from about 10 quality % to 65 quality %, and even more preferably from about 20 quality % to 60 quality %.
The Emulsion acrylic resin (a1-1'(d) of core/shell type hydroxyl) the preparation monomer mixture that can have a polymerizable unsaturated monomer of a polymerizable unsaturated group for the per molecule of the polymerizable unsaturated monomer and about 70 quality % to 99.9 quality % that such as make the per molecule of about 0.1 quality % to 30 quality % have two or more polymerizable unsaturated group carry out the emulsion of letex polymerization formation core multipolymer (I); The monomer mixture of other polymerizable unsaturated monomer of the polymerizable unsaturated monomer of the hydroxyl of about 1 quality % to 40 quality %, the carboxylic hydrophobic polymerizable unsaturated monomer of about 1 quality % to 30 quality %, the hydrophobic polymerizable unsaturated monomer of about 5 quality % to 50 quality % and about 10 quality % to 93 quality % is added in this emulsion; And carry out letex polymerization formation shell multipolymer (II) further.
The emulsion polymerization of the emulsion of core multipolymer (I) can be prepared according to known method.Such as, this emulsion can by using polymerization starter make monomer mixture generation letex polymerization and prepare under the existence of tensio-active agent.
For above-mentioned tensio-active agent, anion surfactant and nonionogenic tenside.The example of anion surfactant comprises sodium salt and the ammonium salt of alkylsulphonic acid, alkane phenylbenzimidazole sulfonic acid, alkylphosphonic acid carboxylic acid etc., the example of nonionogenic tenside comprises polyoxyethylene oleyl ether, polyoxyethylene stearyl base ether, polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene phenyl ether, ethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, Vinlub 73, polyoxyl 40 stearate, Aceonon 300 MO, Sorbitan monolaurate, Stearinsaeure sorbitan ester, Sorbitan Trioleate, polyoxyethylene 20 sorbitan monolaurate etc.
Other example of spendable tensio-active agent comprises the anion surfactant containing polyoxyalkylenes that per molecule has anion-radicals and polyoxyalkylenes such as polyoxyethylene groups or polyoxypropylene base; And per molecule has the reactive anion surfactant of anion-radicals and free radical polymerizable unsaturated group.Wherein, preferred reactive anion surfactant.
The example of reactive anion surfactant comprises the sodium salt of the sulfoacid compound of the free radical polymerizable unsaturated group with such as allyl group, methylallyl, (methyl) acryl, propenyl or butenyl; The ammonium salt etc. of these sulfoacid compounds.Wherein, consider the water-repellancy of the excellence of gained film, preferably there is the ammonium salt of the sulfoacid compound of free radical polymerizable unsaturated group.The example of the ammonium salt of this commercially available sulfoacid compound comprises LATEMUL S-180A (trade(brand)name, KAO. Corp. SA (Kao Corporation) produces).
In the ammonium salt of sulfoacid compound with free radical polymerizable unsaturated group, particularly preferably there is the ammonium salt of the sulfoacid compound of free radical polymerizable unsaturated group and polyoxyalkylenes.The commercially available ammonium salt with the sulfoacid compound of free radical polymerizable unsaturated group and polyoxyalkylenes comprises Aqualon KH-10 (trade(brand)name, 1st industrial pharmaceutical Co., Ltd. (Dai-Ichi KogyoSeiyaku Co., Ltd.) make), LATEMUL PD-104 (trade(brand)name, KAO. Corp. SA's system), Adekaria Soap SR-1025 (trade(brand)name, rising sun electrification company (ADEKA Co., Ltd.) system) etc.
Relative to the total mass of monomer used, the amount of tensio-active agent is preferably about 0.1 quality % to 15 quality %, more preferably from about 0.5 quality % to 10 quality %, and even more preferably from about 1 quality % to 5 quality %.
The example of polymerization starter comprises organo-peroxide, such as benzoyl peroxide, peroxide decoyl, lauroyl peroxide, the acid of peroxidation distearyl, hydrogen phosphide cumene, ditertiary butyl peroxide, two tertiary amyl superoxide, tert-butyl peroxide-2-ethylhexanoate (tert-butyl peroxi-2-ethylhexanoate), the peroxylauric acid tert-butyl ester, t-butylperoxyisopropyl carbonic ether, peroxide acetic acid butyl ester and di-isopropylbenzene hydroperoxide; Azo-compound, such as Diisopropyl azodicarboxylate, azo two (2,4-methyl pentane nitrile), azo two (2-methyl propionitrile (propionenitrile)), azo two (2-methylbutyronitrile), 4,4'-azos two (4-cyano butyric acid), dimethyl azo two (2 Methylpropionic acid ester), azo two [2-methyl-N-(2-hydroxyethyl)-propionic acid amide] and azo pair [2-methyl-N-[2-(1-hydroxybutyl)] propionic acid amide]; Persulphate, such as Potassium Persulphate, ammonium persulphate and Sodium Persulfate etc.These polymerization starters can be used alone or two or more couplings.Can also use by above-mentioned polymerization starter is combined with the reductive agent of such as sugar, sodium sulfoxylate formaldehyde, iron complex etc. the redox initiator etc. prepared.
Usually, relative to the total mass of whole monomer used, the amount of polymerization starter is preferably about 0.1 quality % to 5 quality %, and is more preferably about 0.2 quality % to 3 quality %.The method adding polymerization starter is not particularly limited, and suitably can select according to the type of polymerization starter used and consumption.Such as, in advance polymerization starter can be mixed in monomer mixture or in water medium, or dropwise add when being polymerized or disposablely to add.
The monomer mixture forming shell multipolymer (II) optionally can contain other component, polymerization starter as escribed above, chain-transfer agent, reductive agent and tensio-active agent.Preferably monomer mixture is dropwise added as by monomer mixture being scattered in the monomer emulsion obtained in water medium, but also monomer mixture itself dropwise can be added.In the case, the particle diameter of monomer emulsion is not particularly limited.
The method that polymeric monomer intermixture forms shell multipolymer (II) comprises such as by monomer mixture or its emulsion is disposable or progressively instill in the emulsion of core multipolymer (I), and heats this mixture while stirring to optimal temperature.The Emulsion acrylic resin (a1-1'(d) of the core/shell type hydroxyl of acquisition like this) there is multilayered structure, it contains per molecule and has the core multipolymer (I) that the polymerizable unsaturated monomer of two or more polymerizable unsaturated group and per molecule have the monomer mixture of the polymerizable unsaturated monomer of a polymerizable unsaturated group, and the shell multipolymer (II) of the monomer mixture of the polymerizable unsaturated monomer of hydroxyl, carboxylic hydrophobic polymerizable unsaturated monomer, hydrophobic polymerizable unsaturated monomer and other polymerizable unsaturated monomer.
The Emulsion acrylic resin (a1-1'(d) of the core/shell type hydroxyl of acquisition like this) median size be generally about 10nm to 1,000nm, and preferred about 20nm to 500nm.
In this manual, the Emulsion acrylic resin (a1-1'(d) of core/shell type hydroxyl) median size refer to and use submicron particle size Distribution Analyzer under 20 ° of C, measure the value of acquisition with after deionized water dilution according to conventional methods.Such as can by COULTER N4 (trade(brand)name, BeckmanCoulter, Inc. system) as submicron particle size Distribution Analyzer.
In order to improve the Emulsion acrylic resin (a1-1'(d) of core/shell type hydroxyl) mechanical stability of particle, preferably use in neutralizing agent and the acidic-group of such as carboxyl of water-dispersible acrylic's resin.This neutralizing agent is not particularly limited, if can in and acidic-group.The example of this neutralizing agent comprises sodium hydroxide, potassium hydroxide, Trimethylamine 99,2-(dimethylamino) ethanol, 2-amino-2-methyl-1-propanol, triethylamine, ammoniacal liquor etc.After preferably the amount of this neutralizing agent can make neutralization, the pH value of the aqueous dispersions of water-dispersible acrylic's resin is about 6.5 to about 9.0.
dead front type is containing the carbamate resins emulsion (a1-2 (d)) of isocyanic ester
Dead front type has following characteristic containing the carbamate resins emulsion (a1-2 (d)) of isocyanic ester: this emulsion obtains by making polyisocyanate component and polyol component reaction; This polyisocyanate component contains alicyclic diisocyanate; And polyol component contains the polycarbonate diol relative to polyol component total amount 50 quality % or more.
For the model, consumption etc. of polyisocyanate component and polyol component, can be used in and be used as those of carbamate resins emulsion (a1-1 (c)) initial feed described in embodiment (III).
Can by such as under type introduces the masked isocyanate base of carbamate resins emulsion (a1-2 (d)) that dead front type contains isocyanic ester: excessive polyisocyanate component and polyol component and the amine component that uses as required are reacted, formed containing the urethane copolymers of terminal isocyanate groups, and make to react containing the urethane copolymers of terminal isocyanate groups and encapsulant; Or excessive polyisocyanate component and encapsulant are reacted, and products therefrom and diol component are reacted.
In aforesaid method, proportion of composing is not particularly limited.Can by representing ratio of components with functional group's (being called as isocyanate-reactive group) of isocyanate reaction and the mol ratio of isocyanate group in polyisocyanate component in polyol component during reaction and amine component.The mol ratio of isocyanate-reactive group and isocyanate group is preferably 0.3:1 to 1.0:1, and more preferably 0.5:1 to 0.9:1.If this is the quantity not sufficient of unreacted isocyanate group in polyurethane molecular due to dispersion, then when using as coating composition, the binding property of film and/or intensity may reduce; And if the excessive existence of unreacted isocyanate group, then isocyanate group may affect dispersion stabilization and/or the performance of coating composition.
Relative to the total amount of polyisocyanate component and polyol component, dead front type is preferably 5 quality % to 50 quality % containing the amount of polyisocyanate component in the carbamate resins emulsion (a1-2 (d)) of isocyanic ester, and more preferably 10 quality % to 35 quality %.
Dead front type comprises aliphatic polymeric isocyanate, alicyclic polymeric isocyanate, aliphatic-aromatic polymeric polyisocyanate, aromatic poly-isocyanate and the derivative with blocking agent thereof containing the example of encapsulant in the carbamate resins emulsion (a1-2 (d)) of isocyanic ester.
The example of derivative comprises isocyanuric acid ester, biuret and adducts (such as TMP (trimethyl propane) adducts).
Encapsulant is used for closing free isocyanate group.When the temperature at such as 100 ° of C or higher, and when adding the polyisocyanate compounds of heat-seal at the temperature of preferred 130 ° of C or higher, isocyanate group is reproduced and can easily reacts with hydroxyl.The example of such encapsulant comprises phenol, cresols, xylenol, nitrophenol, ethylphenol, xenol, butylphenol, isopropyl-phenol, nonylphenol, octyl phenol, methyl hydroxybenzoate and similar phenolic compound; ε-caprolactam, δ-Valerolactim, butyrolactam, azetidinone and similar lactam analog compound; Methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, lauryl alcohol and similar fatty alcohol compounds; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, methoxyl group methyl alcohol and similar ether compound; Benzylalcohol; Oxyacetic acid; Methyl glycolate, ethyl glycollate, butyl glycolate and similar ethyl glycolate; Lactic acid, methyl lactate, ethyl lactate, n-Butyl lactate and similar lactate; Methylolurea, melamine methylol, diacetone alcohol, vinylformic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate and similar alcohol compound; Formyl amidoxime, acetyl amidoxime, acetoxime, methyl ethyl ketoxime, Diacetylmonoxime, diphenylketoxime, cyclohexanone-oxime and similar oxime compounds; Dimethyl malonate, diethyl malonate, methyl aceto acetate, methyl acetoacetate, methyl ethyl diketone and similar active methylene group compounds; Butyl sulfhydryl, tert.-butyl mercaptan, hexylmercaptan, tertiary lauryl mercaptan, 2-mercaptobenzothiazole, thiophenol, methylbenzene phenyl-sulfhydrate, ethyl thiophenol and similar sulfur alcohol compound; Acetanilide, methoxyacetanilide, acettoluide, acrylamide, Methacrylamide, ethanamide, stearylamide, benzamide and similar amides; Succinimide, phthalic imidine, maleimide and similar imide analog compounds; The aminated compoundss such as pentanoic, nonox, xylidine, N-phenyl xylidine, carbazole, aniline, naphthylamines, butylamine, dibutylamine, butyl phenyl amine; Imidazoles, 2-ethyl imidazol(e) and similar glyoxaline compound; 3，5-dimethylpyrazole and similar pyrazole compound; Urea, thiocarbamide, ethylidene-urea, ethylene thiourea, sym-diphenylurea and similar carbamide compounds; Phenyl N-phenylcarbamate and similar amino formate compounds; Ethyleneimine, propyleneimine and similar imine compound; Sodium bisulfite, Potassium hydrogen sulfite and similar sulphite compounds.
Wherein, oxime, lactan and pyrazoles encapsulant can suitably be used.Methyl ethyl ketoxime and pyrazole compound are suitable especially to be used, because they can at room temperature store, and can cure at lower temperature (130 ° of C).
Per molecule can there be is the hydroxycarboxylic acid of one or more hydroxyl and one or more carboxyl to be used as partially enclosed dose.The example of hydroxycarboxylic acid comprises hydroxyl trimethylacetic acid and dimethylol propionic acid.
Further, the polyoxyethylene glycol of can be the hydroxyl the other end by one end be methoxyl group is used as partially enclosed dose, to introduce non-ionic hydrophilic thus to give water dispersible.
Relative to containing the isocyanate group of every mole in the urethane polymer of terminal isocyanate groups, the amount of encapsulant is generally 1 equivalent or more and is less than 2 equivalents, and preferred 1.05 equivalent to 1.5 equivalents.
Viscosity preferably adds the solvent as viscosity-depression agent in advance, because can increase between isocyanate group and encapsulant reaction period.Solvent was added before or after the forming reactions of the urethane polymer containing terminal isocyanate groups starts.
The example that can be used as the solvent of viscosity-depression agent comprises aromatic hydrocarbon solvent, esters solvent, ether solvent, ketones solvent, and the mixture of two or more these solvents; But from security and wholesomeness, preferred flash-point is the solvent of 70 ° of C or higher.
In order to carbamate resins emulsion (a1-2 (the d)) dispersiveness making dead front type contain isocyanic ester is stablized, one or more emulsifying agents can be used, such as tensio-active agent.
For the particle diameter etc. of the model of emulsifying agent, consumption, emulsion, the condition of the relevant carbamate resins emulsion (a1-1 (c)) described in embodiment (III) can be used in.
Dead front type can be selected arbitrarily containing the solids content of the carbamate resins emulsion (a1-2 (d)) of isocyanic ester, is not particularly limited.This solids content is preferably 10 quality % to 50 quality %, because the dispersiveness within the scope of this and coating performance are well, and more preferably 20 quality % to 40 quality %.
Consider the chipping resistance of gained film and the paint removing (cleaning capacity) of spray gun, dead front type is 2 containing the weight-average molecular weight of the carbamate resins emulsion (a1-2 (d)) of isocyanic ester, 000 to 50,000, preferably 3,000 to 40,000, and more preferably 5,000 to 30,000.And hydroxyl value can be selected arbitrarily, is not particularly limited, and be generally 0 to 100mg KOH/g.In addition, acid number is preferably 10mg KOH/g to 40mg KOH/g, and more preferably 15mg KOH/g to 30mg KOH/g.
Hydroxyl value and acid number all represent by the amount (mg) of the KOH of every gram of resin consumption.
Dead front type has lower molecular weight containing carbamate resins emulsion (a1-2 (d)) the more common carbamate resins emulsion of isocyanic ester, therefore, compared with common carbamate resins emulsion, excellent spray gun coating detachability etc. is provided.
Consider smoothness and the reflection sharpness of gained multilayer film, relative to the solids content of binder ingredients (a1), in binder ingredients (a1), dead front type is preferably 10 quality % to 98 quality % containing the amount of the carbamate resins emulsion (a1-2 (d)) of isocyanic ester, more preferably 15 quality % to 60 quality %, and even more preferably 15 quality % to 55 quality %.
other film-forming resin
The example being used as other film-forming resin of binder ingredients (a1) together with the carbamate resins emulsion (a1-2 (d)) that can contain isocyanic ester with the Emulsion acrylic resin of hydroxyl (a1-1 (d)) and dead front type comprises except dead front type is containing vibrin, Synolac and the urethane resin except the carbamate resins emulsion (a1-2 (d)) of isocyanic ester.They preferably have crosslinkable functionality, such as hydroxyl, carboxyl and epoxy group(ing).When film-forming resin has hydroxyl, its hydroxyl value is preferably about 1mg KOH/g to 200mg KOH/g, more preferably from about 2mg KOH/g to 180mgKOH/g, and even more preferably from about 5mg KOH/g to 170mg KOH/g.In addition, when film-forming resin has acidic-group such as carboxyl, its acid number is preferably about 5mg KOH/g to 150mg KOH/g, more preferably from about 10mg KOH/g to 100mg KOH/g, and even more preferably from about 15mg KOH/g to 80mg KOH/g.
Consider the smoothness and reflection sharpness, particularly preferably binder ingredients (a1) vibrin containing hydroxyl (a1-3 (d)) of improving film.In this case, relative to the total solids of the Emulsion acrylic resin (a1-1 (d)) of hydroxyl and the vibrin (a1-3 (d)) of hydroxyl, the Emulsion acrylic resin (a1-1 (d)) of hydroxyl is about 10:90 quality % to 90:10 quality % with the ratio of the vibrin (a1-3 (d)) of hydroxyl, and preferred 20:80 quality % to 80:20 quality %.
the vibrin (a1-3 (d)) of hydroxyl
The model, consumption etc. of the vibrin (a1-2) of the hydroxyl described in the first embodiment can be used in the vibrin (a1-3 (d)) of hydroxyl.
linking agent
Except film-forming resin, linking agent also can be used as binder ingredients (a1).When linking agent is used as binder ingredients (a1) a part of, film-forming resin usually can be have such as hydroxyl, carboxyl or epoxy group(ing) crosslinkable functionality and can react with linking agent thus form the resin (matrix resin) of cross-linked coating.
Such as, those linking agents addressed in the first embodiment " linking agent " project can be used as such linking agent.
When water-based colored coating composition (A) is containing linking agent, consider the smoothness and water-repellancy of improving gained multilayer film, its amount is preferably about 5 quality % to 50 quality % relative to the solids content of 100 mass parts binder ingredientss (a1), and more preferably from about 10 quality % to 40 quality %.
pigment (a2)
The type, consumption etc. of the pigment (a2) addressed in the first embodiment also can be used in this embodiment.
the additive of coating composition
If needed, water-based colored coating composition (A) can contain the additive of coating composition, such as thickening material, curing catalysts, UV absorption agent, photostabilizer, defoamer, softening agent, surface conditioner and antisettling agent.
As for the type, consumption etc. of the additive of such coating composition, those that address in the first embodiment can be used.Water-based colored coating composition (A) preparation method addressed in the first embodiment and the condition of coating process also can be used in this embodiment, except binder ingredients (a1) comprises the Emulsion acrylic resin (a1-1 (d)) of hydroxyl and the dead front type carbamate resins emulsion (a1-2 (d)) containing isocyanic ester.
operation (2) is to (4)
For the coating composition, coating process, heating means etc. that use in operation (2) to (4), the condition addressed in the first embodiment also can be used in this embodiment.
According in the method for formation multilayer film of the present invention, even when omitting the preheating procedure after application water-based colored coating composition (A), and when being coated on the painted film containing a large amount of solvent by the water-based paint compositions (B) containing effect pigment, also can form the multilayer film with excellent smoothness, reflection sharpness and water-repellancy.The chances are inhibits the painted film of gained to expand due to water and organic solvent owing to comprising the Emulsion acrylic resin (a1-1 (d)) of hydroxyl and dead front type containing the use of the water-based colored coating composition (A) of the carbamate resins emulsion (a1-2 (d)) of isocyanic ester for this.In addition, application causes being formed on painted film containing water-based paint compositions (B) to the film thickness of effect pigment the film that wherein effect pigment exists with high-density containing a large amount of effect pigment, and this makes the solvent in painted film be difficult in entrance effect film.Further, because the water-based paint compositions (B) containing effect pigment comprises relatively large hydrophobic solvent (b3), the shipwreck in painted film is with in entrance effect film.Due to these reasons, prevent water-based colored coating composition (A) and form mixolimnion containing the water-based paint compositions (B) of effect pigment.In addition, the masked isocyanate base of the reaction that dead front type contains in the carbamate resins emulsion (a1-2 (d)) of isocyanic ester improves the solidified nature of painted film, and improve the binding property of effect film, thus form the multilayer film with excellent chipping resistance.
Embodiment
Hereinafter with reference to embodiment and comparative example, the present invention is described in more detail.But the invention is not restricted to following embodiment.Note, " part " and " % " is all benchmark with quality.
the preparation of the acrylic resin (a1-1 (a)) of hydroxyl
Preparation example A1
By 128 parts of deionized waters and 2 parts of Adekaria Soap SR-1025 (trade(brand)names, ADEKA produces, emulsifying agent, activeconstituents 25%) insert in the reaction vessel with thermometer, thermostatted, whipping appts, reflux exchanger, nitrogen ingress pipe and dropping funnel, be uniformly mixed in stream of nitrogen gas, and be warming up to 80 ° of C.
Then, 1% of following monomer emulsion (1 (a)) total amount and the ammonium persulfate aqueous solution of 5.3 part 6% are added in reaction vessel, and keep 15 minutes under 80 ° of C.Then, in 3 hours, remaining monomer emulsion (1 (a)) instillation is kept in reaction vessel at the same temperature.After dropping terminates, by mixture ageing 1 hour.Then, in 1 hour, following monomer emulsion (2 (a)) is instilled in reaction vessel.After aging 1 hour, in reaction vessel, slowly add 2-(dimethylamino) aqueous ethanolic solution of 40 part 5% and be cooled to 30 ° of C simultaneously, use 100 object nylon cloths to filter, obtain the acrylic resin aqueous dispersions (a1-1-1 (a)) that median size is 100nm, solids content is the water dispersible hydroxyl of 30% thus.The acid number of the acrylic resin of gained water dispersible hydroxyl is 33mg KOH/g, and hydroxyl value is 25mg KOH/g.
Monomer emulsion (1 (a)): 40 parts of deionized waters, 2.8 parts of Adekaria Soap SR-1025,2.1 parts of methylene-bisacrylamides, 2.8 parts of vinylbenzene, 16.1 parts of methyl methacrylates, 28 parts of ethyl propenoates and 21 parts of n-butyl acrylates are mixed and stir, thus obtain monomer emulsion (1 (a)).
Monomer emulsion (2 (a)): 17 parts of deionized waters, 1.2 parts of Adekaria Soap SR-1025,0.03 part of ammonium persulphate, 3 parts of vinylbenzene, 5.1 parts of 2-Hydroxy ethyl acrylates, 5.1 parts of methacrylic acids, 6 parts of methyl methacrylates, 1.8 parts of ethyl propenoates and 9 parts of n-butyl acrylates are mixed and stir, thus obtain monomer emulsion (2 (a)).
Preparation embodiment A 2
35 parts of propylene glycol monopropyl ethers are inserted in the reaction vessel with thermometer, thermostatted, whipping appts, reflux exchanger, nitrogen ingress pipe and dropping funnel, and is warming up to 85 ° of C.Then, dripped wherein in 4 hours and comprise 30 parts of methyl methacrylates, 20 parts of ethyl acrylates, 29 parts of n-butyl acrylates, 15 parts of 2-Hydroxy ethyl acrylates, 6 parts of vinylformic acid, 15 parts of propylene glycol monopropyl ethers and 2.3 part 2, the mixture of 2'-azo two (2,4-methyl pentane nitrile).This mixture ageing 1 hour after dropping terminates.Then, in 1 hour, drip the mixture of 10 parts of propylene glycol monopropyl ethers and 1 part of 2,2'-azo two (2,4-dimethyl-penten eyeball) further wherein.This mixture ageing 1 hour after dropping terminates.Add 7.4 parts of diethanolamine further, obtain the acrylic resin soln (a1-1-2 (a)) that solids content is the hydroxyl of 55% thus.The acid number of the acrylic resin of gained hydroxyl is 47mg KOH/g, and hydroxyl value is 72mg KOH/g.
the preparation of the vibrin (a1-2) of hydroxyl
Preparation embodiment A 3
By 109 parts of TriMethylolPropane(TMP)s, 141 part 1,6-hexylene glycol, 126 part 1,2-cyclohexane dicarboxylic acid acid anhydride and 120 parts of hexanodioic acids are inserted in the reaction vessel with thermometer, thermostatted, whipping appts, reflux exchanger and water separator, mixture was warming up to 160 ° of C to 230 ° of C in 3 hours, then, condensation reaction is carried out 4 hours, simultaneously through the water of condensation of water separator distillation removing generation at 230 ° of C.Then, in order to be introduced in the condensation reaction products of acquisition by carboxyl, in this product, add 38.3 parts of trimellitic acid 1,2-anhydrides, react 30 minutes under 170 ° of C subsequently.Subsequently, this product spent glycol monobutyl ether is diluted, obtain the polyester resin solution (a1-2-1 (a)) that solids content is the hydroxyl of 70% thus.The acid number of the vibrin of the hydroxyl obtained is 46mg KOH/g, and hydroxyl value is 150mg KOH/g, and number-average molecular weight is Isosorbide-5-Nitrae 00.In the composition of initial feed, the total content of the alicyclic polyprotonic acid in acid constituents is 46mol% relative to the total amount of acid constituents.
the preparation of dispersible pigment dispersion
Preparation embodiment A 4
Acrylic resin soln (a1-2-1 (a)), 50 parts of JR-806 (trade(brand)names of the hydroxyl obtained in embodiment A 2 prepared by 18 parts (solids content is 10 parts), TAYCA CORP. produces, rutile titanium dioxide) and 30 parts of deionized waters add and be uniformly mixed in container, and to mix.Subsequently, add 2-(dimethylamino) ethanol wherein, pH value is adjusted to 8.0.Then, the mixing solutions obtained being added capacity is in the wide mouth glass bottle of 225cc.Adding diameter is about granulated glass sphere as dispersion medium, and bottle to be sealed.Mixture is painted agitator and disperse 4 hours, thus obtain dispersible pigment dispersion ((a2-1 (a))).
Preparation embodiment A 5
Acrylic resin soln (a1-1-2 (a)), 25 parts of Barifine BF-1 (trade(brand)names of the hydroxyl obtained in embodiment A 2 prepared by 18 parts (solids content is 10 parts), Sakai ChemicalIndustry Co., Ltd. produce, barium sulfate powder) and 36 parts of deionized waters add and be uniformly mixed in container, and to mix.Subsequently, add 2-(dimethylamino) ethanol wherein, and its pH value is adjusted to 8.0.Then, the mixing solutions obtained being added capacity is in the wide mouth glass bottle of 225cc.In bottle, add diameter is about granulated glass sphere as dispersion medium, and bottle to be sealed.Mixture is painted agitator and disperse 4 hours, thus obtain dispersible pigment dispersion (a2-2 (a)).
Preparation embodiment A 6
Acrylic resin soln (a1-2-1 (a)), 10 parts of Mitsubishi Carbon Black MA-100 (trade(brand)names of the hydroxyl obtained in embodiment A 2 prepared by 18 parts (solids content is 10 parts), Mitsubishi Chemical Corporation produces, carbon black) and 50 parts of deionized waters add and be uniformly mixed in container, and to mix.Subsequently, add 2-(dimethylamino) ethanol wherein, and its pH value is adjusted to 8.0.Then, the mixing solutions obtained being added capacity is in the wide mouth glass bottle of 225cc.In bottle, add diameter is about granulated glass sphere as dispersion medium, and bottle to be sealed.Mixture is painted agitator and disperse 4 hours, thus obtain dispersible pigment dispersion ((a2-3 (a))).
the preparation of water-based colored coating composition (A)
Preparation embodiment A 7
By polyester resin solution (a1-2-1 (a)), 37.5 parts of Cymel325 (trade(brand)names of the hydroxyl of acquisition in the acrylic resin aqueous dispersions (a1-1-1 (a)) of the water dispersible hydroxyl of acquisition in 80 parts of preparation embodiment A 1,42 parts of preparation embodiment A 3, Japan Cytec Industries, Inc. produce; Melamine resin; Solids content 80%), the dispersible pigment dispersion (a2-1 (a)) obtained in 157 parts of preparation embodiment A 4 and 4 parts of dispersible pigment dispersions (a2-3 (a)) preparing acquisition in embodiment A 6 mix.Subsequently to wherein adding ACRYSOL ASE-60 (trade(brand)name, Rohm & Haas Co. produces, Polyacrylate thickeners), 2-(dimethylamino) ethanol and deionized water, thus obtain that pH value is 8.0, solids concn is 45% and be the water-based colored coating composition (A-1 (a)) of 40 seconds by the viscosity that Ford cup No.4 measures under 20 ° of C.
Preparation embodiment A 8 to 10
The method obtaining water-based colored coating composition (A-2 (a)) to (A-4 (a)) is identical with the method preparing embodiment A 7 except using formula shown in following table 1.
Table 1
the vibrin (b1-2) of hydroxyl
Preparation embodiment A 11
111 parts of TriMethylolPropane(TMP)s, 143 part of 1,6-hexylene glycol, 50 part of 1,2-cyclohexane dicarboxylic acid acid anhydride, 100 parts of m-phthalic acids and 106 parts of hexanodioic acids are inserted in the reaction vessel with thermometer, thermostatted, whipping appts, reflux exchanger and water separator.Mixture was heated to 160 ° of C to 230 ° of C in 3 hours, carries out condensation reaction 4 hours at 230 ° of C subsequently, simultaneously through the water of condensation of water separator distillation removing generation.Then, in order to be introduced in the condensation reaction products of acquisition by carboxyl, in this product, add 38 parts of trimellitic acid 1,2-anhydrides, react 30 minutes under 170 ° of C subsequently.Subsequently this product spent glycol monobutyl ether is diluted, obtain the polyester resin solution (b1-2-1 (a)) that solids content is the hydroxyl of 70% thus.The acid number of the vibrin of the hydroxyl obtained is 46mg KOH/g, and hydroxyl value is 151mg KOH/g, and number-average molecular weight is 1,350.In the composition of initial feed, in acid constituents, the total content of alicyclic polyprotonic acid is 17mol% relative to the total amount of acid constituents.
the preparation of effect pigment dispersion liquid
Preparation embodiment A 12
Be uniformly mixed in container, by 22 parts of (solids content is 16 parts) GX-180A (trade(brand)name, the production of Asahi Kasei Metals Co., Ltd., aluminium pigment slurry; Metal content: 74%), the resin solution (see note 1) of 40 parts of 2-ethyl-1-hexanols, 8 parts of (solids content is 4 parts) phosphoric acid and 0.2 part of 2-(dimethylamino) ethanol mixes, thus obtain effect pigment dispersion liquid (b2-1 (a)).The resin solution of (note 1) phosphoric acid: the mixed solvent containing 27.5 parts of methoxypropanol and 27.5 parts of isopropylcarbinols to be inserted in the reaction vessel with thermometer, thermostatted, agitator, reflux exchanger, nitrogen ingress pipe and dropping funnel and to be warming up to 110 ° of C.Subsequently, 25 parts of vinylbenzene will be comprised in 4 hours, 27.5 part n-BMA, higher alkyl acrylic esters (the trade(brand)name: Isostearyl Acrylate of 20 parts of side chains, Osaka Organic Chemical Industry, Ltd. produce), 7.5 parts of 4-hydroxyl butyl propyleneglycol acid esters, the polymerisable monomer (see note 2) of 15 parts of phosphoric acid, 12.5 parts of 2-methacryloxyethyl acid phosphoric acid esters, 10 parts of isopropylcarbinols and 4 parts of t-butylperoxy octylate add in above-mentioned mixed solvent, dripped wherein containing 0.5 part of t-butylperoxy octylate and 20 parts of Virahols in 1 hour subsequently, then aging 1 hour is stirred, thus obtain the resin solution that solids content is the phosphoric acid of 50%.The resin of phosphoric acid is 83mg KOH/g based on the acid number of phosphate, and hydroxyl value is 29mg KOH/g, and weight-average molecular weight is 10,000.
The polymerisable monomer of (note 2) phosphoric acid: 57.5 parts of mono phosphoric acid ester butyl esters and 41 parts of isopropylcarbinols to be inserted in the reaction vessel with thermometer, thermostatted, agitator, reflux exchanger, nitrogen ingress pipe and dropping funnel and to be warming up to 90 ° of C.Then in 2 hours, 42.5 parts of glycidyl methacrylate are dripped.After stirring aging 1 hour, add 59 parts of Virahols wherein, thus obtain the polymerisable monomer solution that solids concn is the phosphoric acid of 50%.Gained monomer is 285mg KOH/g based on the acid number of phosphate.
Preparation embodiment A 13 to A21
The preparation method of effect pigment dispersion liquid (b2-2 (a)) to (b2-10 (a)) is identical with the method prepared in embodiment A 12 except using formula shown in following table 2.
Table 2
containing the preparation of the water-based paint compositions (B) of effect pigment
Preparation embodiment A 22
By the polyester resin solution (a1-2-1 (a)) obtained in the acrylic resin aqueous dispersions (a1-1-1 (a)) of the water dispersible hydroxyl obtained in 100 parts of preparation embodiment A 1,51 parts of preparation embodiment A 3,70 parts of effect pigment dispersion liquids (b2-1 (a)) and 37.5 parts of Cymel325 (trade(brand)names preparing to obtain in embodiment A 12, Japan Cytec Industries, Inc. produce; Melamine resin; Solids content: 80%) mix.Then, add ACRYSOLASE-60 (trade(brand)name wherein, Rohm & Haas Co. produces, Polyacrylate thickeners), 2-(dimethylamino) ethanol and deionized water, thus the water-based paint compositions (B-1 (a)) obtained containing effect pigment, its pH is 8.0, solids concn is 25%, and is 40 seconds by the viscosity that Ford cup No.4 measures under 20 ° of C.
Preparation embodiment A 23 to A36
Obtain the method for the water-based paint compositions (B-2 (a)) to (B-15 (a)) containing effect pigment except using the formula shown in following table 3 identical with the method prepared in embodiment A 22 except solids concn.
Table 3
the preparation of test board 1
The water-based paint compositions (B-1 (a)) containing effect pigment obtained in the water-based colored coating composition (A-1 (a)) to (A-4 (a)) and preparation embodiment A 22 to A36 obtained in preparation embodiment A 7 to A10 is used to prepare test board to (B-15 (a)) in the following manner.Carry out evaluation test subsequently.
treat the preparation of the test coated article 1 of application
By electro dipping cation electric deposition paint composition (trade(brand)name Elecron GT-10 on the cold-rolled steel sheet with zinc phosphate process, Kansai Paint Co., Ltd produces) make to solidify rear film thickness and reach 20 μm, and within 30 minutes, be cured by heating under 170 ° of C, thus the test coated article of application is treated in preparation.
Embodiment A 1
Use rotary-atomizing type electrostatic atomizer, by water-based colored coating composition (A-1 (a)) electrostatic coating of acquisition in preparation embodiment A 7 on above-mentioned test coated article, making to solidify rear film thickness is 20 μm, places 3 minutes.Then rotary-atomizing type electrostatic atomizer is used, by water-based paint compositions (B-1 (a)) electrostatic coating containing effect pigment of acquisition in preparation embodiment A 22 on uncured painted film, making to solidify rear film thickness is 12 μm, place 2 minutes, and preheating 3 minutes under 80 ° of C.Then, by top layer clear coating composition (the trade(brand)name Magicron KINO-1210 based on acryloid, Kansai Paint Co., Ltd produces, hereafter being sometimes referred to as " clear coating composition (C-1) ") electrostatic coating is on uncured effect film, making to solidify rear film thickness is 35 μm, places after 7 minutes, heats 30 minutes under 140 ° of C, to solidify painted film, effect film and transparent coating simultaneously, thus prepare test board.
Embodiment A 2 to A12 and Comparative Example A An 1 to A5
The method preparing test board is identical with embodiment A 1, replaces the water-based colored coating composition (A-1 (a)) obtained in preparation embodiment A 7 except using the arbitrary water-based colored coating composition (A-1 (a)) to (A-4 (a)) shown in following table 4; The arbitrary water-based paint compositions (B-2 (a)) to (B-17 (a)) containing effect pigment shown in following table 4 is used to replace the water-based paint compositions (B-1 (a)) containing effect pigment obtained in preparation embodiment A 22; And it is as shown in table 4 below coating composition to be coated with film thickness after being filled to solidification.
evaluation test 1
According to following test method, the test board obtained in embodiment A 1 to A12 and Comparative Example A An 1 to A5 is evaluated.Evaluation result is as shown in table 4.
test method 1
Smoothness: evaluate smoothness based on the Wc value measured by Wave Scan DOI (trade(brand)name, BYK Gardner produces).Wc value is less, and the smoothness in application face is higher.
Reflection sharpness: evaluate reflection sharpness based on the Wb value measured by Wave Scan DOI (trade(brand)name, BYK Gardner produces).Wb value is less, and the reflection sharpness in application face is higher.
Water-repellancy: to be immersed by brassboard in the water of 40 ° of C 240 hours, takes out, under 20 ° of C dry 12 hours.Then, with the multilayer film on cutters cross cut test board until arrive coated article, 100 grids (2mm x2mm) are formed.Then, scotch tape is attached on the surface of Box Section, tears off suddenly under 20 ° of C.Detect the state of remaining film square.
A: remaining 100 grids, and there is not little edge breakage at the notching edge that cutters cut in film.
B: remaining 100 grids, but film has little edge breakage at the notching edge that cutters cut.
C: remaining 90 to 99 grids.
D: remaining number of squares is less than and equals 89.
Table 4
the preparation of Emulsion acrylic resin
Preparation Embodiment B 1
By 130 mass parts deionized waters and 0.52 mass parts Aqualon KH-10 (trade(brand)name, tensio-active agent, Dai-Ichi Kogyo Seiyaku Co., Ltd. produce) insert in the reaction vessel with thermometer, thermostatted, agitator, reflux exchanger and dropping funnel, stir in nitrogen gas stream and mix, and being warming up to 80 ° of C.Then, by 1% of following monomer emulsion (1 (b)) total amount and 5.3 6% ammonium persulfate solution of mass parts add in reaction vessel, keep 15 minutes under 80 ° of C.Then, in 3 hours, remaining monomer emulsion (1 (b)) instillation is kept in reaction vessel at the same temperature.By mixture ageing 1 hour after dropping terminates.Then, by following monomer emulsion (2 (b)) instillation reaction vessel in 1 hour, aging 1 hour subsequently.Then, mixture is cooled to 30 ° of C, and slowly add the aqueous dimethylethanolamine of 5% of 40 mass parts simultaneously, 100 object nylon cloths are used to filter, thus acquisition median size is 100nm (use COULTER N4 type submicron particle size Distribution Analyzer (Beckman Coulter, Inc. produce), measure under 20 ° of C with deionized water dilution mixture thing), solids concn be 30% Emulsion acrylic resin (A).The acid number of gained acrylic resin is 33mg KOH/g, and hydroxyl value is 25mg KOH/g.
Monomer emulsion (1 (b)): 42 mass parts deionized waters, 0.72 mass parts AqualonKH-10,2.1 mass parts methylene-bisacrylamides, 2.8 mass parts vinylbenzene, 16.1 mass parts methyl methacrylates, 28 mass parts ethyl propenoates and 21 mass parts n-butyl acrylates are mixed and stir, thus obtain monomer emulsion (1 (b)).
Monomer emulsion (2 (b)): 18 mass parts deionized waters, 0.31 mass parts AqualonKH-10,0.03 mass parts ammonium persulphate, 5.1 mass parts methacrylic acids, 5.1 mass parts 2-hydroxyethyl acrylates, 3 mass parts vinylbenzene, 6 mass parts methyl methacrylates, 1.8 mass parts ethyl propenoates and 9 mass parts n-butyl acrylates are mixed and stir, thus obtain monomer emulsion (2 (b)).
the preparation of polyester resin solution
Preparation Embodiment B 2
By 109 mass parts TriMethylolPropane(TMP)s, 141 mass parts 1,6-hexylene glycol, 126 mass parts 1,2-hexahydrophthalic acid and 120 mass parts hexanodioic acids are inserted in the reaction vessel with thermometer, thermostatted, whipping appts, reflux exchanger and water separator, mixture was warming up to 160 ° of C to 230 ° of C in 3 hours, then, under 230 ° of C, condensation reaction 4 hours is carried out.Then, in order to be introduced in the condensation reaction products of acquisition by carboxyl, in this product, add 38.3 mass parts trimellitic acid 1,2-anhydrides, react 30 minutes under 170 ° of C subsequently.Subsequently, diluted by this product spent glycol monobutyl ether, obtaining solids concn is thus the polyester resin solution of 70%.The acid number of the vibrin obtained is 46mg KOH/g, and hydroxyl value is 150mg KOH/g, and weight-average molecular weight is 6,400.In this manual, term " weight-average molecular weight " refers to by gel permeation chromatography (GPC), the value determined by the typical curve of stdn polystyrene).
the preparation of aqueous urethane resin dispersion liquid
Preparation Embodiment B 3
By 115.5 number average molecular weights 2, poly adipate succinic acid ester, the 115.5 number average molecular weights 2 of 000, the polycaprolactone glycol of 000,23.2 parts of dimethylol propionic acids, 6.5 part 1,4-butyleneglycol and 120.1 parts of isophorone diisocyanates are inserted in the reaction vessel with thermometer, thermostatted, whipping appts, reflux exchanger and dropping funnel, stir in nitrogen gas stream and mix, and the 85 ° of C that heat up.Reaction carries out 7 hours, thus acquisition NCO content is the prepolymer of 4.0%.Prepolymer is cooled to 50 ° of C, and 165 parts of acetone are added in this mixture, be uniformly dissolved.Then, while stirring 15.7 parts of triethylamines are added in this mixture, then temperature is maintained 50 ° of C or following time 600 parts of deionized waters are added in this mixture.By gained aqueous dispersions after 50 ° of C maintain 2 hours and complete water expansion reaction, reclaim under reduced pressure acetone under 70 ° of C; Use triethylamine and deionized water adjustment solids content to 30% respectively, pH value to 8, thus obtain acid number and be 26mg KOH/g and median size is the aqueous urethane resin dispersion liquid of 140nm.
the preparation of tinting pigment dispersion liquid
Preparation Embodiment B 4
Being loaded by 350 parts of propylene glycol monopropyl ethers has in the reaction vessel of thermometer, thermostatted, whipping appts, reflux exchanger and dropping funnel, flows down be warming up to 115 ° of C at nitrogen.Then will containing by advance 10 parts of Diisopropyl azodicarboxylates being dissolved in 10 parts of Light EsterPM (trade(brand)names in 3 hours, Kyoeisha Chemical, Co., Ltd., (2-methacryloxyethyl) acid phosphoric acid ester) in obtain mixture solution instillation following monomer mixture in.Gained mixture is maintained this temperature in aging 2 hours further simultaneously.To use subsequently in the dimethylethanolamine of equivalent and gained mixture, add 450 parts of propylene glycol monopropyl ethers, and by dimethylethanolamine adjust ph to 7.5.Thus obtain that acid number is 50mg KOH/g, hydroxyl value is 50mg KOH/g, glass transition temp is 50 ° of C, weight-average molecular weight is 45,000 and solids content is the acrylic resin soln of 55 quality %.
Monomer mixture
By 50 mass parts TITANIX JR-903 (trade(brand)name, the production of TAYCA Co., Ltd.; Surface is through the rutile titanium dioxide of aluminum oxide and zirconium white process), 9 mass parts acrylic resin solns, 45 mass parts deionized waters and 3.9 parts of AMP-95 (trade(brand)name, Dow ChemicalCo. produces; 2-amino-2-methyl-1-propanol; Activeconstituents: 95%) insert in 225ml bottle (mayonnaise bottle), subsequently, the granulated glass sphere being 1.5mm by 130 mass parts diameters is put into wherein, is sealed by bottle.Mixture oscillatory type paint conditioner is disperseed 120 minutes.After dispersion, with 100 object wire screen filtering mixts to remove granulated glass sphere, thus obtain tinting pigment dispersion liquid.Detect the tinting pigment dispersion liquid obtained with grindometer (method A), confirm the coarse particle being more than or equal to 10 μm without size.
the preparation of concentrated flake (Scale-Like) aluminium pigment solution
Preparation Embodiment B 7
In stainless steel beaker, by 135 parts of aluminum paste GX-180A (trade(brand)name, Asahi KaseiMetals, Ltd. production; Flake aluminium pigment slurry; Solids content: 74 quality %) and 130 mass parts ethylene glycol monobutyl ethers stir and mix.
the preparation of matrix coating composition 1
Preparation Embodiment B 8
With in the stainless steel mixing vessel of whipping appts, by the tinting pigment dispersion liquid 1 of acquisition in the aqueous urethane resins obtained in the Emulsion acrylic resin obtained in 100 parts of preparation Embodiment B 1,50 parts of polyester resin solutions preparing to obtain in Embodiment B 2,100 parts of preparation Embodiment B 3,182.5 parts of preparation Embodiment B 4 and 37.5 parts of Cymel325 (trade(brand)names, Japan Cytec Industries, Inc. produce; Melamine resin; Solids content: 80%) mix.Then, add wherein Primal ASE-60 (trade(brand)name, Rohm & Haas Co. produces; Polyacrylate thickeners), 2-(dimethylamino) ethanol and deionized water, thus prepare matrix coating composition 1, its pH is 8.0, and coating composition solids content is 25%, and is 40 seconds by the viscosity that Fordcup No.4 measures under 20 ° of C; And relative to the resin solid content of 100 mass parts, containing 65 mass parts titanium oxide pigments.
Use rotary-atomizing type electrostatic atomizer, 20 ° of C temperature and 65% humidity condition under, by matrix coating composition 1 electrostatic coating that obtains on the flat tin plate of prior degreasing, making to solidify rear film thickness is 20 μm.After application 30 seconds, strike off a part for film, weigh, and under 110 ° of C dry 1 hour.After the application determined by calculating heating residue, the solids content of 30 seconds is 55%.And at 0.1sec -1shearing rate and 23 ° of C temperature condition under after the application that measures the viscosity of 30 seconds be 70,000mPaS.
the preparation of matrix coating composition 2
Preparation Embodiment B 9
With in the stainless steel mixing vessel of whipping appts, by the tinting pigment dispersion liquid 1 of acquisition in the aqueous urethane resin dispersion liquids obtained in the Emulsion acrylic resin obtained in 70 parts of preparation Embodiment B 1,35 parts of polyester resin solutions preparing to obtain in Embodiment B 2,100 parts of preparation Embodiment B 3,182.5 parts of preparation Embodiment B 4 and 25 parts of Cymel325 (trade(brand)names, Japan Cytec Industries, Inc. produce; Melamine resin; Solids content: 80%) mix.Then, add wherein Primal ASE-60 (trade(brand)name, Rohm & Haas Co. produces; Polyacrylate thickeners), 2-(dimethylamino) ethanol and deionized water, thus prepare matrix coating composition 2, its pH is 8.0, and coating composition solids content is 25%, and is 40 seconds by the viscosity that Fordcup No.4 measures under 20 ° of C; And relative to the resin solid content of 100 mass parts, containing 65 mass parts titanium oxide pigments.
Use rotary-atomizing type electrostatic atomizer, 20 ° of C temperature and 65% humidity condition under, by matrix coating composition 2 electrostatic coating that obtains on the flat tin plate of prior degreasing, making to solidify rear film thickness is 20 μm.After application 30 seconds, strike off a part for film, weigh, and under 110 ° of C dry 1 hour.After the application determined by calculating heating residue, the solids content of 30 seconds is 55%.Further, at 0.1sec -1shearing rate and 23 ° of C temperature condition under after the application that measures the viscosity of 30 seconds be 200,000mPaS.
the preparation of matrix coating composition 3
Preparation Embodiment B 10
With in the stainless steel mixing vessel of whipping appts, by tinting pigment dispersion liquid 1, the 6 parts of Cymel325 (trade(brand)names obtained in the aqueous urethane resin dispersion liquid obtained in the polyester resin solution obtained in the Emulsion acrylic resin obtained in 70 parts of preparation Embodiment B 1,35 parts of preparation Embodiment B 2,100 parts of preparation Embodiment B 3,182.5 parts of preparation Embodiment B 4, Japan Cytec Industries, Inc. produce; Melamine resin; Solids content: (trade(brand)name Bayhydrol VPLS2310, Sumika Bayel Urethane Co., Ltd. produces 80%) and 52 parts of dead front type polyisocyanate compounds (B3-1); Solids content: 38%) mix.Then, add wherein Primal ASE-60 (trade(brand)name, Rohm & Haas Co. produces; Polyacrylate thickeners), 2-(dimethylamino) ethanol and deionized water, thus prepare matrix coating composition A, its pH is 8.0, and coating composition solids content is 25%, and is 40 seconds by the viscosity that Ford cup No.4 measures under 20 ° of C; And relative to the resin solid content of 100 mass parts, containing 65 mass parts titanium oxide pigments.
Use rotary-atomizing type electrostatic atomizer, 20 ° of C temperature and 65% humidity condition under, by matrix coating composition 3 electrostatic coating that obtains on the flat tin plate of prior degreasing, making to solidify rear film thickness is 20 μm.After application 30 seconds, strike off a part for film, weigh, and under 110 ° of C dry 1 hour.After the application determined by calculating heating residue, the solids content of 30 seconds is 56%.Further, at 0.1sec -1shearing rate and 23 ° of C temperature condition under after the application that measures the viscosity of 30 seconds be 210,000mPaS.
the preparation of matrix coating composition 4
Preparation Embodiment B 11
With in the stainless steel mixing vessel of whipping appts, the concentrated laminar aluminium pigment solution that the polyester resin solution obtained in the Emulsion acrylic resin obtained in 75 parts of preparation Embodiment B 1,40 parts of preparation Embodiment B 2,53.1 mass parts are prepared to obtain in Embodiment B 5 and 37.5 parts of Cymel325 (trade(brand)names, Japan Cytec Industries, Inc. produce; Melamine resin; Solids content: 80%) mix.Then, add Primal ASE-60 (trade(brand)name wherein, Rohm & Haas Co. produces, Polyacrylate thickeners), 2-(dimethylamino) ethanol and deionized water, thus prepare matrix coating composition 4, its pH is 8.0, and coating composition solids content is 25%, and is 40 seconds by the viscosity that Ford cup No.4 measures under 20 ° of C; And relative to the resin solid content of 100 mass parts, containing 20 mass parts flake aluminium pigment.
the preparation of matrix coating composition 5
Preparation Embodiment B 12
With in the stainless steel mixing vessel of whipping appts, the concentrated laminar aluminium pigment solution that the polyester resin solution obtained in the Emulsion acrylic resin obtained in 100 parts of preparation Embodiment B 1,50 parts of preparation Embodiment B 2,31.8 mass parts are prepared to obtain in Embodiment B 5 and 37.5 parts of Cymel325 (trade(brand)names, Japan Cytec Industries, Inc. produce; Melamine resin; Solids content: 80%) mix.Then, add wherein Primal ASE-60 (trade(brand)name, Rohm & Haas Co. produces; Polyacrylate thickeners), 2-(dimethylamino) ethanol and deionized water, thus prepare matrix coating composition 5, its pH is 8.0, and coating composition solids content is 25%, and is 40 seconds by the viscosity that Ford cup No.4 measures under 20 ° of C; And relative to the resin solid content of 100 mass parts, based on solid, containing 12 mass parts flake aluminium pigment.
the test preparation of coated article 2
At steel plate (the JIS G3141 through degreasing and zinc phosphate process, be of a size of 400x300x0.8mm) on by electrodeposition coating cation electric deposition paint composition (trade(brand)name Elecron9400HB, Kansai Paint Co., Ltd produces, containing epoxy resin/based on the resin cation (R.C.) of polyamine and dead front type polyisocyanate compounds as solidifying agent) to make to solidify rear film thickness be 20 μm, heat 20 minutes and crosslinking curing under 170 ° of C.The obtained product forming electrodeposition coating is thereon used as test coated article.
Embodiment B 1
Use rotary-atomizing type electrostatic atomizer, on the test coated article that matrix coating composition 1 (b) electrostatic coating obtained in preparation Embodiment B 8 is prepared in above-mentioned " preparation of test coated article 2 ", making to solidify rear film thickness is 20 μm, places 3 minutes.Then, use rotary-atomizing type electrostatic atomizer, by matrix coating composition 4 (b) electrostatic coating that obtains in preparation Embodiment B 11 on uncured matrix coating composition 1 (b), making to solidify rear film thickness is 7 μm, place 2 minutes, and preheating 3 minutes under 80 ° of C.Then, by MagicronKINO-1210 (trade(brand)name, Kansai Paint Co., Ltd produces, top layer clear coating composition based on acryloid) on the film that formed at uncured matrix coating composition 4 (b) of electrostatic coating, making to solidify rear film thickness is 35 μm, place after 7 minutes, heat 30 minutes under 140 ° of C, with while the film that formed of cured matrix coating composition 1 film, the matrix coating composition 4 that are formed and transparent coating, thus prepare test board.
Embodiment B 2 to B9 and comparative example B1
Except using the composition shown in table 5, the preparation method of brassboard is identical with Embodiment B 1.
Table 5
Comparative example B2
Use rotary-atomizing type electrostatic atomizer, on the test coated article that matrix coating composition 1 (b) electrostatic coating obtained in preparation Embodiment B 8 is prepared in above-mentioned " preparation of test coated article 2 ", making to solidify rear film thickness is 20 μm, place 3 minutes, and preheating 3 minutes under 80 ° of C.Then, use rotary-atomizing type electrostatic atomizer, on the film that matrix coating composition 5 (b) electrostatic coating obtained in preparation Embodiment B 12 is formed at uncured matrix coating composition 1, making to solidify rear film thickness is 15 μm, place 2 minutes, and preheating 3 minutes under 80 ° of C.Then, by Magicron KINO-1210 (trade(brand)name, Kansai Paint Co., Ltd's production; Top layer clear coating composition based on acryloid) on the film that formed at uncured matrix coating composition 2 of electrostatic coating, making to solidify rear film thickness is 35 μm, place after 7 minutes, heat 30 minutes under 140 ° of C, with while the film that formed of cured matrix coating composition 1 film, the matrix coating composition 5 that are formed and transparent coating, thus prepare test board.
evaluation test 2
the solids content of 30 seconds and viscosity after application
Table 5 shows solids content after 30 seconds of composition application in the preparation of test board in Embodiment B 1 to B9 and comparative example B1 and B2 and viscosity.
test method 2
Reflection sharpness: evaluate based on the Wb value measured by Wave Scan DOI (trade(brand)name, BYK Gardner produces).Wb value is the index of the amplitude of the wavelength lower surface roughness of about 0.3mm to 1mm.Wb value is less, and the reflection sharpness in application face is higher.
Water-repellancy: the test coated article being used in preparation in " preparation of test coated article 2 ", and test its water-repellancy by identical method and judgement criteria in above-mentioned test method 1.
the preparation of carbamate resins emulsion (a1-1)
Preparation Embodiment C 1
By 67.2 parts of UMC (1/1), (Ube Industries, Ltd. produce; Containing 1,6-hexylene glycol and 1,4-cyclohexanedimethanol is as the polycarbonate diol of diol component, 1,6-hexylene glycol and 1, the mass ratio of 4-cyclohexanedimethanol is 1:1) and 4.5 parts of dimethylolpropionic acids insert in the reaction vessel with thermometer, thermostatted, whipping appts, reflux exchanger and water separator, and stirring while be warming up to 80 ° of C.When temperature reaches 80 ° of C, in 1 hour, instill 28.3 parts of dicyclohexyl methyl hydride-4,4'-vulcabond.Then, 29.9 parts of N-Methyl pyrrolidone are added wherein, and by aging under 80 ° of C further for the mixture obtained, to complete the reaction forming carbamate.When isocyanate value reaches 3.0 or lower, stop heating, and under 70 ° of C, 3.27 parts of triethylamines are added in mixture.Subsequently, 200 parts of deionized waters, while 50 ° of C, instilled to be dispersed in water by mixture in this mixture by holding temperature in 1 hour, thus obtained carbamate resins emulsion (a1-1-1 (c)).The solids content of the carbamate resins emulsion (a1-1-1 (c)) obtained is 30%, and weight-average molecular weight is 29,000, and acid number is 21mgKOH/g, and median size is 100nm.
Preparation Embodiment C 2 to C10
Using the composition shown in table 6, obtaining carbamate resins emulsion (a1-1-2 (c)) to (a1-1-10 (c)) by synthesizing in the mode identical with preparation Embodiment C 1.Note, in table 6, (* 1) to (* 10) refers to following content:
(* 1) UMC (1/1): containing 1,6-hexylene glycol and the 1,4 cyclohexane dimethanol polycarbonate diol as diol component, the mass ratio of 1,6-hexylene glycol and 1,4 cyclohexane dimethanol is 1:1; UbeIndustries, Ltd. produce.
(* 2) UMC (3/1): containing 1,6-hexylene glycol and the 1,4 cyclohexane dimethanol polycarbonate diol as diol component, the mass ratio of 1,6-hexylene glycol and 1,4 cyclohexane dimethanol is 3:1; UbeIndustries, Ltd. produce.
(* 3) UMC (1/3): containing 1,6-hexylene glycol and the 1,4 cyclohexane dimethanol polycarbonate diol as diol component, the mass ratio of 1,6-hexylene glycol and 1,4 cyclohexane dimethanol is 1:3; UbeIndustries, Ltd. produce.
(* 4) UH100: containing the polycarbonate diol of 1,6-hexylene glycol as diol component; UbeIndustries, Ltd. produce.
(* 5) UC100: containing the polycarbonate diol of 1,4 cyclohexane dimethanol as diol component; Ube Industries, Ltd. produce.
(* 6) PEG1000: polyoxyethylene glycol; Molecular weight: 1,000; Sanyo Chemical Industries, Ltd. produce.
(* 7) DMPA: dimethylol propionic acid
(* 8) Isosorbide-5-Nitrae BD:1,4-butyleneglycol
(* 9) IPDI: isophorone diisocyanate
(* 10) hydrogenation MDI:4,4'-dicyclohexyl methane diisocyanate
Table 6
the preparation of the acrylic resin (a1-2 (c)) of hydroxyl
Preparation Embodiment C 11
By the acrylic resin aqueous dispersions (a1-1-1 (a)) by preparing water dispersible hydroxyl prepared by method described in embodiment A 1 as following (a1-2 (c)).
Preparation Embodiment C 12
By the acrylic resin soln (a1-2-2 (c)) of the acrylic resin soln (a1-1-2 (a)) of the hydroxyl by method acquisition described in preparation embodiment A 2 as following hydroxyl.
The preparation of the vibrin (a1-3 (c)) of hydroxyl
Preparation Embodiment C 13
By the polyester resin solution (a1-3-1 (c)) of the polyester resin solution (a1-3-1 (a)) of the hydroxyl by method acquisition described in preparation embodiment A 3 as following hydroxyl.
the preparation of dispersible pigment dispersion
Preparation Embodiment C 14
By the dispersible pigment dispersion (a2-1 (a)) by method acquisition described in preparation embodiment A 4 as following dispersible pigment dispersion (a2-1 (c)).
Preparation Embodiment C 15
By the dispersible pigment dispersion (a2-2 (a)) by method acquisition described in preparation embodiment A 5 as following dispersible pigment dispersion (a2-2 (c)).
Preparation Embodiment C 16
By the dispersible pigment dispersion (a2-3 (a)) by method acquisition described in preparation embodiment A 6 as following dispersible pigment dispersion (a2-3 (c)).
the preparation of water-based colored coating composition (A)
Preparation Embodiment C 17
100 parts are prepared polyester resin solution (a1-3-1 (c)), 25 parts of Cymel325 (trade(brand)names of the hydroxyl of acquisition in the acrylic resin aqueous dispersions (a1-2-1 (c)) of the water dispersible hydroxyl obtained in the carbamate resins emulsion (a1-1-1 (c)) obtained in Embodiment C 1,80 parts of preparation Embodiment C 11,20 parts of preparation Embodiment C 13, Japan Cytec Industries, Inc. produce; Melamine resin; Solids content 80%), the dispersible pigment dispersion (a2-1 (c)) obtained in 157 parts of preparation Embodiment C 14 and 4 parts of dispersible pigment dispersions (a2-3 (c)) preparing acquisition in Embodiment C 16 mix.Subsequently, add wherein ACRYSOL ASE-60 (trade(brand)name, Rohm & HaasCo. produces; Polyacrylate thickeners), 2-(dimethylamino) ethanol and deionized water, thus obtain that pH value is 8.0, solids concn is 45% and be the water-based colored coating composition (A-1 (c)) of 40 seconds by the viscosity that Ford cup No.4 measures under 20 ° of C.
Preparation Embodiment C 18 to C28
Except using the formula shown in table 7, obtain water-based colored coating composition (A-2 (c)) to (A-12 (c)) by preparation method identical in Embodiment C 17.
Table 7
the preparation of the vibrin (b1-2) of hydroxyl
Preparation Embodiment C 29
By the polyester resin solution (b1-2-1 (c)) of the polyester resin solution (b1-2-1 (a)) of the hydroxyl by method acquisition described in preparation embodiment A 11 as following hydroxyl.
the preparation of effect pigment dispersion liquid
Preparation Embodiment C 30 to C39
By the effect pigment dispersion liquid (b2-1 (a)) to (b2-10 (a)) that obtained by method described in preparation embodiment A 12 to A21 as following dispersible pigment dispersion (b2-1 (c)) to (b2-10 (c)).
containing the preparation of the water-based paint compositions (B) of effect pigment
Preparation Embodiment C 40 to C54
By the water-based paint compositions (B-1 (a)) to (B-15 (a)) containing effect pigment that obtained by method described in preparation embodiment A 22 to A36 as the following water-based paint compositions (B-1 (c)) containing effect pigment to (B-15 (c)).
the preparation of test board 3
By the water-based colored coating composition (A-1 (c)) to (A-12 (c)) obtained in preparation Embodiment C 17 to C28 and the water-based paint compositions (B-1 (c)) to (B-15 (c)) containing effect pigment that obtains in preparation Embodiment C 40 to C54 for the preparation of test board.Carry out evaluation test subsequently.
Embodiment C 1 to C21 and comparing embodiment C1 to C9
Identical with described in embodiment A 1 of the preparation method of test board and above-mentioned " treating the preparation of the test coated article 1 of application ", except using the water-based colored coating composition (A-1 (c)) obtained in preparation Embodiment C 17 to C28 to (A-12 (c)), and the water-based paint compositions (B-1 (c)) containing effect pigment obtained in preparation Embodiment C 40 to C54 is to (B-15 (c)); And film thickness is as shown in table 8 below after coating process composition to solidification.
evaluation test 3 and test method 3
By the method described in above-mentioned test method 1 to the smoothing degree of test board obtained in above-described embodiment C1 to C21 and comparing embodiment C1 to C5, reflection sharpness and waterproofing property evaluation.Evaluation result is as shown in table 8.
Table 8
the preparation of the Emulsion acrylic resin (a1-1 (d)) of hydroxyl
Preparation embodiment D1
By 120 parts of deionized waters and 0.8 part of Adekaria Soap SR-1025 (trade(brand)name, ADEKA production; Emulsifying agent, activeconstituents: 25%) insert in the reaction vessel with thermometer, thermostatted, whipping appts, reflux exchanger, nitrogen ingress pipe and dropping funnel, stir in a stream of nitrogen and mix, and be warming up to 80 ° of C subsequently.Then, 5% of following monomer emulsion (1-1 (d)) total amount and the ammonium persulfate aqueous solution of 2.5 part 6% are added in reaction vessel, and keep 15 minutes under 80 ° of C.Then, in 3 hours, remaining monomer emulsion (1-1 (d)) instillation is kept in reaction vessel at the same temperature.By mixture ageing 1 hour after instillation terminates.Then, by following monomer emulsion (2-1 (d)) instillation reaction vessel in 1 hour, aging 1 hour subsequently.Then mixture is cooled to 30 ° of C, and slowly add 2-(dimethylin) aqueous ethanolic solution of 3.8 part 5% simultaneously, use 100 object nylon cloths to filter, to obtain median size be thus 100nm and solids content is the Emulsion acrylic resin (a1-1-1 (d)) of the hydroxyl of 30%.The acid number of the Emulsion acrylic resin of the hydroxyl obtained is 24mgKOH/g, and hydroxyl value is 11mg KOH/g.
Monomer emulsion (1-1 (d)): by 54.0 parts of deionized waters, 3.1 parts of Adekaria SoapSR-1025,31.2 parts of n-butyl acrylates, 31.2 parts of methyl methacrylates, 12.3 parts of vinylbenzene and 2.3 parts of allyl methacrylate(AMA) mix and blends, thus obtain monomer emulsion (1-1 (d)).
Monomer emulsion (2-1 (d)): by 50.0 parts of deionized waters, 1.8 parts of Adekaria SoapSR-1025,0.04 part of ammonium persulphate, 9.2 parts of n-butyl acrylates, 4.0 parts of methyl methacrylates, 3.7 parts of vinylbenzene, 2.3 parts of 2-Hydroxyethyl acrylates and 3.7 parts of methacrylic acid mix and blends, thus obtain monomer emulsion (2-1 (d)).
Preparation embodiment D2
Except using monomer emulsion (2-2 (d)) to replace monomer emulsion (2-1 (d)), with the mode acrylic acid synthesizing emulsion (a1-1-2 (d)) identical with preparation embodiment D1.The median size of the Emulsion acrylic resin (a1-1-2 (d)) of hydroxyl is 100nm, and solids content is 30%, and acid number is 10mgKOH/g, and hydroxyl value is 10.5mg KOH/g.
Monomer emulsion (2-2 (d)): by 50.0 parts of deionized waters, 1.8 parts of Adekaria SoapSR-1025,0.04 part of ammonium persulphate, 9.2 parts of n-butyl acrylates, 6.1 parts of methyl methacrylates, 3.7 parts of vinylbenzene, 2.3 parts of 2-Hydroxyethyl acrylates and 1.6 parts of methacrylic acid mix and blends, thus obtain monomer emulsion (2-2 (d)).
Preparation embodiment D3
Except using monomer emulsion (2-3 (d)) to replace monomer emulsion (2-1 (d)), with the mode acrylic acid synthesizing emulsion (a1-1-3 (d)) identical with preparation embodiment D1.Obtain that median size is 100nm, solids content is 30%, acid number is 0.65mg KOH/g and hydroxyl value is the Emulsion acrylic resin (a1-1-3 (d)) of the hydroxyl of 11mg KOH/g.
Monomer emulsion (2-3 (d)): by 50.0 parts of deionized waters, 1.8 parts of Adekaria SoapSR-1025,0.04 part of ammonium persulphate, 9.2 parts of n-butyl acrylates, 7.7 parts of methyl methacrylates, 3.7 parts of vinylbenzene, 2.3 parts of 2-Hydroxyethyl acrylates and 0.1 part of methacrylic acid mix and blend, thus obtain monomer emulsion (2-3 (d)).
Preparation embodiment D4
By 120 parts of deionized waters and 0.8 part of Adekaria Soap SR-1025 (trade(brand)name, ADEKA production; Emulsifying agent; Activeconstituents: 25%) insert in the reaction vessel with thermometer, thermostatted, whipping appts, reflux exchanger, nitrogen ingress pipe and dropping funnel, stir in a stream of nitrogen and mix, and be warming up to 80 ° of C.Then, 5% of following monomer emulsion (1-2 (d)) total amount and the ammonium persulfate aqueous solution of 2.5 part 6% are added in reaction vessel, keep 15 minutes under 80 ° of C.Then, in 3 hours, remaining monomer emulsion (1-2 (d)) instillation is kept in reaction vessel at the same temperature.After instillation terminates, by mixture ageing 1 hour.Then, mixture is cooled to 30 ° of C, and slowly add 2-(dimethylin) aqueous ethanolic solution of 3.8 part 5% simultaneously, use 100 object nylon cloths to filter, obtain median size thus and be 100nm and solids content is the Emulsion acrylic resin (a1-1-4 (d)) of the hydroxyl of 30%.The acid number of the acrylic resin of the water dispersible hydroxyl of gained is 24mg KOH/g, and hydroxyl value is 11mg KOH/g.
Monomer emulsion (1-2 (d)): 104.2 parts of deionized waters, 4.9 parts of Adekaria SoapSR-1025,0.04 part of ammonium persulphate, 37.8 parts of n-butyl acrylates, 37.9 parts of methyl methacrylates, 16.0 parts of vinylbenzene, 2.3 parts of allyl methacrylate(AMA)s, 2.3 parts of 2-Hydroxyethyl acrylates and 3.68 parts of methacrylic acids are mixed and stir, thus obtain monomer emulsion (1-2 (d)).
the preparation of carbamate resins emulsion (a1-2 (d))
Preparation embodiment D5
30.1 parts of hydrogenation MDI and 1.5 part methyl ethyl ketone oxime (methylethylketoxim) are inserted in the reaction vessel with thermometer, thermostatted, whipping appts, reflux exchanger and water separator, be warming up to 80 ° of C, and stir 1 hour, thus obtain isocyanate reaction product.64/1 part of UM90 (1/1) (participating in following (* 1)) and 4.2 parts of dimethylol propionic acids are inserted in separator, is heated to 80 ° of C and stirs content simultaneously.When temperature reaches 80 ° of C, in 1 hour, isocyanate reaction product is dropwise added.Then, 29.9 parts of N-Methyl pyrrolidone are added wherein, and by aging under 80 ° of C further for the mixture obtained, to complete the reaction forming carbamate.When isocyanate value reaches 3.0 or lower, stop heating, and under 70 ° of C, 2.75 parts of triethylamines are added in this mixture.Subsequently, 200 parts of deionized waters, while 50 ° of C, instilled to be dispersed in water by mixture in mixtures by holding temperature in 1 hour, thus obtained carbamate resins emulsion (a1-2-1 (d)).The solids content of the carbamate resins emulsion (a1-2-1 (d)) obtained is 30%, and acid number is 19.9mg KOH/g, and weight-average molecular weight is 11,300, and is 77nm by the particle diameter of dynamic light scattering determination.
Preparation embodiment D6 to D18
Using the composition shown in table 9, obtaining carbamate resins emulsion (a1-2-2 (d)) to (a1-2-14 (d)) in the mode identical with preparation embodiment D5 by synthesizing.
Note, as mentioned above, (* 11) to (* 14) refer to following content for (* 4) to (* 7) in table, (* 9) and (* 10):
(* 11) UM90 (1/1): containing 1,4 cyclohexane dimethanol and 1, the 6-hexylene glycol polycarbonate diol as diol component, the mass ratio of 1,4 cyclohexane dimethanol and 1,6-hexylene glycol is 1:1; Ube Industries, Ltd. produce.
(* 12) UM90 (3/1): containing 1,4 cyclohexane dimethanol and 1, the 6-hexylene glycol polycarbonate diol as diol component, the mass ratio of 1,4 cyclohexane dimethanol and 1,6-hexylene glycol is 3:1; Ube Industries, Ltd. produce.
(* 13) UM90 (1/3): containing 1,4 cyclohexane dimethanol and 1, the 6-hexylene glycol polycarbonate diol as diol component, the mass ratio of 1,4 cyclohexane dimethanol and 1,6-hexylene glycol is 1:3; Ube Industries, Ltd. produce.
(* 14) aminosilane: N-β (amino-ethyl) gamma-amino propyl trimethoxy silicane.
Table 9
the preparation of the vibrin (a1-3) of hydroxyl
Preparation embodiment D19
The polyester resin solution (a1-2-1 (a)) of the hydroxyl obtained in method described in above-mentioned preparation embodiment A 3 is as the polyester resin solution (a1-3-1 (d)) of following hydroxyl.
the preparation of dispersible pigment dispersion
Preparation embodiment D20
The dispersible pigment dispersion (a2-1 (a)) obtained in method described in above-mentioned preparation embodiment A 4 is as following dispersible pigment dispersion (a2-1 (d)).
Preparation embodiment D21
The dispersible pigment dispersion (a2-2 (a)) obtained in method described in above-mentioned preparation embodiment A 5 is as following dispersible pigment dispersion (a2-2 (d)).
Preparation embodiment D22
The dispersible pigment dispersion (a2-3 (a)) obtained in method described in above-mentioned preparation embodiment A 6 is as following dispersible pigment dispersion (a2-3 (d)).
the preparation of water-based colored coating composition (A)
Preparation embodiment D23
100 parts are prepared polyester resin solution (a1-3-1 (d)), 25 parts of Cymel325 (trade(brand)names of the hydroxyl obtained in the polyester resin emulsion (a1-1-2 (d)) of the hydroxyl obtained in the carbamate resins emulsion (a1-2-1 (d)) obtained in embodiment D5,80 parts of preparation embodiment D2,20 parts of preparation embodiment D19, Japan Cytec Industries, Inc. produce; Melamine resin; Solids content 80%), in 157 parts of preparation embodiment D20, the dispersible pigment dispersions (a2-1 (a)) that obtain and 4 parts are prepared the dispersible pigment dispersion (a2-3 (d)) obtained in embodiment D22 and are mixed.Subsequently, add wherein ACRYSOL ASE-60 (trade(brand)name, Rohm & HaasCo. produces; Polyacrylate thickeners), 2-(dimethylamino) ethanol and deionized water, thus obtain that pH value is 8.0, solids concn is 45% and be the water-based colored coating composition (A-1 (d)) of 40 seconds by the viscosity that Ford cup No.4 measures under 20 ° of C.
Preparation embodiment D24 to D42
Except using the formula shown in table 10, obtain water-based colored coating composition (A-2 (d)) to (A-20 (d)) in the mode identical with preparation embodiment D23.
Table 10
the preparation of the vibrin (b1-2) of hydroxyl
Preparation embodiment D43
By the polyester resin solution (b1-2-1 (a)) of hydroxyl that obtains in method described in above-mentioned preparation embodiment A 11 polyester resin solution (b1-2-1 (d)) as following hydroxyl.
the preparation of effect pigment dispersion liquid
Preparation embodiment D44 to D53
By the effect pigment dispersion liquid (b2-1 (a)) to (b2-10 (a)) that obtains in method described in above-mentioned preparation embodiment A 12 to A21 as following dispersible pigment dispersion (b2-1 (d)) to (b2-10 (d)).
containing the preparation of the water-based paint compositions (B) of effect pigment
Preparation embodiment D54 to D68
By the water-based paint compositions (B-1 (a)) to (B-15 (a)) containing effect pigment that obtains in method described in above-mentioned preparation embodiment A 22 to A36 as the following water-based paint compositions (B-1 (d)) containing effect pigment to (B-15 (d)).
the preparation of test board 4
The water-based paint compositions (B-1 (d)) containing effect pigment obtained in the water-based colored coating composition (A-1 (d)) to (A-20 (d)) and preparation embodiment D54 to D68 obtained in preparation embodiment D23 to D42 is used to prepare test board to (B-15 (d)) in the following manner.Carry out evaluation test subsequently.
Embodiment D1 to D29 and comparing embodiment D1 to D5
Except using the water-based paint compositions (B-1 (d)) containing effect pigment obtained in the water-based colored coating composition (A-1 (d)) to (A-20 (d)) and preparation embodiment D54 to D68 that obtain in preparation embodiment D23 to D42 to (B-15 (d)), and coating process composition to make to solidify rear film thickness as shown in table 11 below, prepare test board in the mode identical with embodiment A 1 with above-mentioned " treating the preparation of the test coated article 1 of application ".
evaluation test 4
According to the test board obtained in following testing method Evaluation operation example D1 to D29 and comparing embodiment D1 to D5.Evaluation result is in table 11.
testing method 4
Smoothness: measured and evaluation test plate by the method described in above-mentioned testing method 1.
Reflection sharpness: evaluate reflection sharpness based on the Wb value measured by Wave Scan DOI (trade(brand)name, BYK Gardner produces).Wb value is less, and the reflection sharpness in application face is higher.
Chipping resistance: test board is placed on the specimen holder of the test set that bursts apart (production of trade(brand)name JA-400, SugaTest Instruments Co., Ltd.), uses 0.392MPa (4kgf/cm at the temperature of-20 ° of C 2) pressurized air, blow to test board from the place of distance test (DT) plate 30cm with the 50g granite stones of the angle of 30 degree by No. 7 granularity.Afterwards, the washing of gained test board is also dry, in coated face adhesive fabric adhesive tape (production of Nichiban Co., Ltd.).Then, peel off above-mentioned adhesive tape, visual observation also evaluates the situation of the cut that film is formed.
A: the size of cut is little, the steel plate of galvanic deposit face and coated article does not all expose.
B: the size of cut is little, but the steel plate of galvanic deposit face and coated article exposes.
C: the size of cut is very large, and the steel plate of coated article exposes on a large scale.
Table 11

Claims (13)

1. form the method for multilayer film, carry out following operation (1) ~ (4) successively:
(1) application water-based colored coating composition (A) on coated article, forms uncured painted film;
(2) the described uncured painted film do not formed in preheating procedure (1), binder ingredients (b1) is comprised to described uncured painted film application, the water-based paint compositions (B) containing effect pigment of effect pigment (b2) and hydrophobic solvent (b3), after forming solidification, film thickness is the uncured effect film of 7 μm to 13 μm, wherein, relative to the solids content of the described binder ingredients (b1) of 100 mass parts, effect pigment (b2) is 15 mass parts to 30 mass parts, hydrophobic solvent (b3) is 25 mass parts to 60 mass parts,
(3) to described uncured effect film transparent paint coating composition (c) formed in operation (2), uncured transparent coating is formed; And
(4) described uncured painted film, described uncured effect film and the described uncured transparent coating that are formed in the operation (1) to (3) respectively of heating, solidifies that this is three-layer coated simultaneously,
Wherein said water-based colored coating composition (A) comprises binder ingredients (a1) and pigment (a2), described binder ingredients (a1) comprises use polyisocyanate component and polyol component is 2 as weight-average molecular weight prepared by starting raw material, 000 to 50, the carbamate resins emulsion (a1-1 (c)) of 000, described polyisocyanate component comprises alicyclic diisocyanate, and relative to described polyol component total amount, described polyol component comprises the polycarbonate diol of 50 quality % or more, or
Wherein said water-based colored coating composition (A) comprises binder ingredients (a1) and pigment (a2), described binder ingredients (a1) comprise Emulsion acrylic resin (a1-1 (d)) that acid number is 25mg KOH/g or less hydroxyl and dead front type containing isocyanic ester carbamate resins emulsion (a1-2 (d)) as it at least partially, wherein, described dead front type uses the polyol component of the polyisocyanate component containing alicyclic diisocyanate and the polycarbonate diol containing 50 quality % or more to be prepared from as starting raw material containing the carbamate resins emulsion (a1-2 (d)) of isocyanic ester.
2. the method forming multilayer film as claimed in claim 1, the solids content of the wherein said water-based paint compositions (B) containing effect pigment is 18 quality % to 35 quality %.
3. the method forming multilayer film as claimed in claim 1, wherein said water-based colored coating composition (A) comprises binder ingredients (a1) and titanium dioxide and/or barium sulfate, and the solids content of described binder ingredients (a1) relative to 100 mass parts, the total content of titanium dioxide and barium sulfate is 50 mass parts to 150 mass parts.
4. the method forming multilayer film as claimed in claim 1, wherein said binder ingredients (b1) comprises the vibrin of hydroxyl as it at least partially, wherein relative to the total content of acid constituents in its starting raw material, the content of alicyclic polyprotonic acid is 20mol% to 100mol%.
5. the method forming multilayer film as claimed in claim 1, wherein when 20 DEG C temperature and 65% humidity under water-based colored coating composition (A) described in application thus after making solidification, the thickness of film is 20 μm time, described water-based colored coating composition (A) solids content of 30 seconds after its application is 45% to 65%, and after its application 30 seconds at 23 DEG C, 0.1sec -1shearing rate under the viscosity that measures be 50,000mPas to 500,000mPas.
6. the method forming multilayer film as claimed in claim 5, a part for the resin Composition as binder ingredients of wherein said water-based colored coating composition (A) is aqueous urethane resin.
7. the method forming multilayer film as claimed in claim 1, wherein said polycarbonate diol obtains by making diol component and the reaction of carbonyl agent, relative to described diol component total amount, described diol component comprises the glycol with 6 or more carbon atoms of 90 quality % or more, and described in there are 6 or more carbon atoms glycol comprise the alicyclic diol containing ring alkylidene group with 6 or more carbon atoms.
8. the method forming multilayer film as claimed in claim 1, wherein said pigment (a2) comprises titanium dioxide and/or barium sulfate, and the solids content of described binder ingredients (a1) relative to 100 mass parts, the total content of titanium dioxide and barium sulfate is 50 mass parts to 150 mass parts.
9. the method forming multilayer film as claimed in claim 1, the Emulsion acrylic resin (a1-1 (d)) of wherein said hydroxyl is Structure of Core/shell Emulsion, it has core part and shell part, described core part is multipolymer (I), the per molecule of polymerizable unsaturated monomer and 70 quality % to 99.9 quality % that the per molecule comprising 0.1 quality % to 30 quality % has two or more polymerizable unsaturated groups has the polymerizable unsaturated monomer of a polymerizable unsaturated group as copolymer component, and described shell part is multipolymer (II), comprise the polymerizable unsaturated monomer of the hydroxyl of 1 quality % to 40 quality %, the carboxylic polymerizable unsaturated monomer of 1 quality % to 30 quality % and other polymerizable unsaturated monomer of 30 quality % to 98 quality % are as copolymer component.
10. the method forming multilayer film as claimed in claim 1, wherein said dead front type is 2,000 to 50,000 containing the weight-average molecular weight of the carbamate resins emulsion (a1-2 (d)) of isocyanic ester.
11. methods forming multilayer film as claimed in claim 1, wherein said polycarbonate diol obtains by making diol component and the reaction of carbonyl agent, relative to described diol component total amount, described diol component comprises the glycol with 6 or more carbon atoms of 90 quality % or more, and described in there are 6 or more carbon atoms glycol comprise the alicyclic diol containing ring alkylidene group with 6 or more carbon atoms.
12. methods forming multilayer film as claimed in claim 1, wherein said pigment (a2) comprises titanium dioxide and/or barium sulfate, and the solids content of described binder ingredients (a1) relative to 100 mass parts, the total content of titanium dioxide and barium sulfate is 50 mass parts to 150 mass parts.
13. article, it comprises the film formed by the method for the formation multilayer film described in claim arbitrary in claim 1 to 12.
CN201180032092.6A 2010-07-02 2011-06-29 Method for forming multilayer coating film Active CN102959019B (en)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
JP2010-152504 2010-07-02
JP2010152504 2010-07-02
JP2010-156933 2010-07-09
JP2010156933 2010-07-09
JP2010180372 2010-08-11
JP2010-180372 2010-08-11
JP2011007734 2011-01-18
JP2011-007734 2011-01-18
PCT/JP2011/065418 WO2012002569A1 (en) 2010-07-02 2011-06-29 Method for forming multilayer coating film

Publications (2)

Publication Number Publication Date
CN102959019A CN102959019A (en) 2013-03-06
CN102959019B true CN102959019B (en) 2015-05-13

Family

ID=44504102

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201180032092.6A Active CN102959019B (en) 2010-07-02 2011-06-29 Method for forming multilayer coating film

Country Status (5)

Country Link
US (1) US8758896B2 (en)
JP (1) JP5680109B2 (en)
CN (1) CN102959019B (en)
GB (1) GB2492934B (en)
WO (1) WO2012002569A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110461955A (en) * 2017-03-31 2019-11-15 巴斯夫涂料有限公司 The method for forming multilayer film

Families Citing this family (60)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105105911B (en) * 2010-06-18 2018-10-23 花王株式会社 The manufacturing method of heater
JP5870939B2 (en) * 2011-02-10 2016-03-01 宇部興産株式会社 Aqueous polyurethane resin dispersion and use thereof
WO2012108491A1 (en) * 2011-02-10 2012-08-16 宇部興産株式会社 Waterborne polyurethane resin dispersion and use thereof
CN103459048B (en) * 2011-04-06 2015-05-27 关西涂料株式会社 Method for forming multi-layered coating film
KR102070467B1 (en) 2011-12-28 2020-01-29 도레이 카부시키가이샤 Multilayer film for decorative molding, polyurethane resin, and method for producing decorative molded body
WO2013126185A1 (en) * 2012-02-21 2013-08-29 U.S. Coatings Ip Co. Llc Low foaming waterborne coating composition and use thereof
JP5885828B2 (en) * 2012-02-24 2016-03-16 関西ペイント株式会社 Multilayer coating film forming method and coated article
JP6208120B2 (en) * 2012-03-22 2017-10-04 日本ペイント・オートモーティブコーティングス株式会社 Multi-layer coating formation method
JP6416078B2 (en) * 2012-03-30 2018-10-31 スリーエム イノベイティブ プロパティズ カンパニー Protective coating for low refractive index materials
CN104204116B (en) * 2012-04-04 2016-06-29 关西涂料株式会社 The manufacture method of water-based paint compositions and coated article
JP6067006B2 (en) * 2012-05-24 2017-01-25 関西ペイント株式会社 Water-based coating composition, multilayer coating film forming method, and article having multilayer coating film
JP5948164B2 (en) 2012-06-28 2016-07-06 Ｂａｓｆジャパン株式会社 Multi-layer coating formation method
JP5688571B2 (en) * 2013-02-04 2015-03-25 日本ペイント株式会社 Multi-layer coating formation method
EP3031840A4 (en) * 2013-08-07 2016-12-28 Japan Coating Resin Corp Polyurethane, urethane-(meth)acrylate composite resin, and aqueous urethane-(meth)acrylate composite resin dispersion
JP2015093901A (en) * 2013-11-11 2015-05-18 アイカ工業株式会社 Aqueous coating material composition
EP2886570A1 (en) * 2013-12-18 2015-06-24 BASF Coatings GmbH Aqueous coating agent and production of multilayer coatings using the coating agent
JP6764402B2 (en) 2014-07-03 2020-09-30 コーニング インコーポレイテッド Jet ink compositions, methods and coated articles
KR101679683B1 (en) * 2014-12-24 2016-11-28 주식회사 케이씨씨 High elastic polyester modified urethane resin and clearcoat composition containing thereof
CA2974183C (en) 2015-01-29 2020-09-22 Kansai Paint Co., Ltd. Method for forming multilayer coating film
JP6567566B2 (en) * 2015-01-30 2019-08-28 関西ペイント株式会社 Multi-layer coating formation method
JP2018052997A (en) * 2015-02-12 2018-04-05 関西ペイント株式会社 Surface-coated brilliant pigment and brilliant coating composition containing the same
EP3297773B1 (en) * 2015-05-22 2021-06-09 BASF Coatings GmbH Aqueous base paint for making a coating
JP6732014B2 (en) 2015-05-22 2020-07-29 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ Manufacturing method of multi-coat coating
JP6330743B2 (en) * 2015-07-08 2018-05-30 マツダ株式会社 Laminated coatings and painted products
WO2017058504A1 (en) * 2015-10-02 2017-04-06 Resinate Materials Group, Inc. High performance coatings
MX2018007797A (en) * 2015-12-25 2018-08-15 Kansai Paint Co Ltd Multilayer coating film forming method.
JP6928599B2 (en) 2016-02-22 2021-09-01 株式会社カネカ Polyol composition and thermosetting resin
US10412767B2 (en) 2016-04-20 2019-09-10 Futurewei Technologies, Inc. System and method for initial attachment in a communications system utilizing beam-formed signals
EP3486291B1 (en) * 2016-07-13 2022-12-07 Kansai Paint Co., Ltd Effect pigment dispersion
US11459463B2 (en) 2016-11-18 2022-10-04 Kansai Paint Co., Ltd. Method for forming multilayer coating film
US11344914B2 (en) * 2016-11-18 2022-05-31 Kansai Paint Co., Ltd. Method for forming multi-layer coating film
JP6859014B2 (en) * 2016-11-23 2021-04-14 関西ペイント株式会社 Multi-layer coating film forming method
JP6466977B2 (en) * 2017-02-15 2019-02-06 トヨタ自動車株式会社 Multi-layer coating formation method
JP7090399B2 (en) * 2017-02-21 2022-06-24 日本ペイント・オートモーティブコーティングス株式会社 Water-based paint composition and multi-layer coating
JP6833016B2 (en) 2017-03-29 2021-02-24 関西ペイント株式会社 Multi-layer coating film forming method
JP6628761B2 (en) * 2017-03-31 2020-01-15 日本ペイント・オートモーティブコーティングス株式会社 Method of forming multilayer coating film
KR101979995B1 (en) * 2017-05-25 2019-05-17 주식회사 케이씨씨 Water soluable paint kit for vehicle
JP2019044073A (en) * 2017-09-01 2019-03-22 宇部興産株式会社 Emulsion composition
CN111093841A (en) * 2017-09-26 2020-05-01 关西涂料株式会社 Method for forming multilayer coating film
WO2019109022A1 (en) 2017-11-30 2019-06-06 Moore John R Coating compositions for application utilizing a high transfer efficiency applicator and methods and systems thereof
CN111511553B (en) * 2017-12-15 2022-12-27 关西涂料株式会社 Laminated body
CN111615431B (en) * 2018-01-15 2022-05-06 关西涂料株式会社 Method for forming multilayer coating film
US20190255789A1 (en) 2018-02-22 2019-08-22 Ronald L. Meline Transparency repair system
US11541420B2 (en) * 2018-05-09 2023-01-03 Kansai Paint Co., Ltd. Method for forming multilayer coated film
US10840953B2 (en) * 2018-07-18 2020-11-17 Ppg Industries Ohio, Inc. Coated articles demonstrating electromagnetic radiation transparency and method of mitigating contaminant build-up on a substrate
US10954408B2 (en) * 2018-07-18 2021-03-23 Ppg Industries Ohio, Inc. Curable film-forming compositions prepared from multiple hydrophobic polymers and method of mitigating dirt build-up on a substrate
JP6826095B2 (en) * 2018-12-21 2021-02-03 日本ペイント・オートモーティブコーティングス株式会社 Multi-layer coating film forming method
US20210394233A1 (en) * 2019-02-01 2021-12-23 Hewlett-Packard Development Company, L.P. Printed foam panels for electronic devices
KR20210145190A (en) * 2019-03-26 2021-12-01 도요보 가부시키가이샤 laminated polyester film
MX2021001704A (en) * 2019-05-30 2021-04-19 Nippon Paint Automotive Coatings Co Ltd Multilayer coating film forming method.
CN110305508B (en) * 2019-06-12 2021-07-02 广东邦宁新材料科技有限公司 Preparation method of polyborosiloxane modified polyurethane water-based paint
WO2021018735A1 (en) * 2019-07-29 2021-02-04 Basf Coatings Gmbh Process for producing a multilayer coating comprising a sparkling coat layer and multilayer coating obtained from said process
EP4013822A1 (en) 2019-08-12 2022-06-22 BASF Coatings GmbH Method for producing effect pigment pastes using a vibrator
WO2021095760A1 (en) * 2019-11-13 2021-05-20 関西ペイント株式会社 Aqueous coating composition, coated article, and method for forming multilayer coating film
CN115003767A (en) * 2020-02-27 2022-09-02 关西涂料株式会社 Aqueous coating composition and method for forming multilayer coating film
WO2021171705A1 (en) * 2020-02-27 2021-09-02 関西ペイント株式会社 Aqueous coating composition and method for forming multilayer coating film
CN115135734A (en) * 2020-02-28 2022-09-30 日涂汽车涂料有限公司 Aqueous coating composition and method for forming multilayer coating film
JP2021138819A (en) * 2020-03-04 2021-09-16 関西ペイント株式会社 Coating composition and multi-layered coating film formation method
US20230302493A1 (en) * 2020-07-29 2023-09-28 Kansai Paint Co., Ltd. Method for forming multi-layer coating film
CN112251864B (en) * 2020-09-25 2022-06-07 江西金源纺织有限公司 Wear-resistant improved viscose composite yarn and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002003791A (en) * 2000-06-23 2002-01-09 Toyota Central Res & Dev Lab Inc Aqueous coating material
WO2009014226A2 (en) * 2007-07-24 2009-01-29 Kansai Paint Co., Ltd. Method for formin multila er coatin film
WO2009157588A1 (en) * 2008-06-24 2009-12-30 Kansai Paint Co., Ltd. Method for forming multilayer coating film

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2966891B2 (en) * 1990-06-06 1999-10-25 セイコー化成株式会社 Suede-like finishing agent
JP4416147B2 (en) * 2000-12-13 2010-02-17 旭化成ケミカルズ株式会社 Polyurethane emulsion and synthetic leather and artificial leather produced using the same
JP4674962B2 (en) * 2000-12-13 2011-04-20 旭化成ケミカルズ株式会社 Polyurethane emulsion
JP2003251276A (en) 2002-02-28 2003-09-09 Nippon Paint Co Ltd Method of forming multilayered coating film and water based intermediate coating material composition
JP4094912B2 (en) 2002-09-09 2008-06-04 関西ペイント株式会社 Multi-layer coating formation method
WO2007043633A2 (en) * 2005-10-11 2007-04-19 Kansai Paint Co., Ltd. Effect pigment-containing, water-borne base coating compositions
GB2453045B (en) * 2007-09-19 2012-05-30 Kansai Paint Co Ltd Automobile water-based paint
JP5586160B2 (en) * 2008-04-02 2014-09-10 関西ペイント株式会社 Water-based paint composition
JP2010152504A (en) 2008-12-24 2010-07-08 Osaka Prefecture Univ Commodity shelf arrangement device
JP2010156933A (en) 2009-01-05 2010-07-15 Nakamura Mfg Co Ltd Genuineness indicator plate
JP5493372B2 (en) 2009-02-09 2014-05-14 凸版印刷株式会社 Hard coat liquid and hard coat film
JP2011007734A (en) 2009-06-29 2011-01-13 Nikon Corp Encoder and method of attaching the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002003791A (en) * 2000-06-23 2002-01-09 Toyota Central Res & Dev Lab Inc Aqueous coating material
WO2009014226A2 (en) * 2007-07-24 2009-01-29 Kansai Paint Co., Ltd. Method for formin multila er coatin film
WO2009157588A1 (en) * 2008-06-24 2009-12-30 Kansai Paint Co., Ltd. Method for forming multilayer coating film

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110461955A (en) * 2017-03-31 2019-11-15 巴斯夫涂料有限公司 The method for forming multilayer film

Also Published As

Publication number Publication date
GB201220552D0 (en) 2013-01-02
WO2012002569A1 (en) 2012-01-05
GB2492934A (en) 2013-01-16
US20130089731A1 (en) 2013-04-11
JP5680109B2 (en) 2015-03-04
CN102959019A (en) 2013-03-06
US8758896B2 (en) 2014-06-24
JP2013535311A (en) 2013-09-12
GB2492934B (en) 2018-07-25

Similar Documents

Publication Publication Date Title
CN102959019B (en) Method for forming multilayer coating film
CN102317386B (en) Water-based coating composition and method of forming multilayered coating film
CN102471630B (en) Water-based coating composition and method for forming multilayer coating film
CN102597028B (en) Copolymer, aqueous coating composition containing copolymer, and method for forming multilayer coating film
CN102281958B (en) Multilayer coating film-forming method
JP6049747B2 (en) Multi-layer coating formation method
CN101392138B (en) Automobile water-based paint
CN102395630B (en) Base coat paint composition
US9475957B2 (en) Aqueous paint composition and method of manufacturing painted article
JP5451207B2 (en) Water-based coating composition and multilayer coating film forming method
CN104321395A (en) Aqueous paint composition and method for forming coating
WO2015114963A1 (en) Aqueous coating composition
JP5791846B2 (en) Water-based paint composition and coated article
CN104136134A (en) Multilayer film-forming method and coated article
JP4676165B2 (en) Water-based coating composition and multilayer coating film forming method
JP5603177B2 (en) Copolymer, aqueous coating composition containing the copolymer, and method for forming a multilayer coating film
JP2017101233A (en) Intermediate coating composition
JP6448026B2 (en) Multi-layer coating formation method
JP7355968B1 (en) Water-based coating composition, coating film forming method, and multilayer coating film forming method
JP7246489B2 (en) Multi-layer coating film forming method
WO2024018708A1 (en) Aqueous coating material composition, method for forming coating film, and method for forming multilayer coating film
WO2023181492A1 (en) Aqueous coating material composition and method for forming multilayer coating film

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant